Fluid Phase Equilibria 302 (2011) 6573

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Fluid Phase Equilibria

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

Properties and phase equilibria of uid mixtures as the basis for developing
green chemical processes
Richard L. Smith Jr. a,b, , Zhen Fang c
a
b
c

Graduate School of Environmental Studies, Research Center of Supercritical Fluid Technology, Tohoku University, Aramaki Aza Aoba 6-6-11, Aoba-ku, Sendai 980-8579, Japan
Department of Chemical Engineering, Tohoku University, Aramaki Aza Aoba 6-6-11, Aoba-ku, Sendai 980-8579, Japan
Chinese Academy of Sciences, Biomass Group, Xishuangbanna Tropical Botanical Garden, 88 Xuefulu, Kunming, Yunnan Province 650223, China

a r t i c l e

i n f o

Article history:
Received 27 May 2010
Received in revised form
26 September 2010
Accepted 26 September 2010
Available online 12 October 2010
Keywords:
High temperature water
Supercritical uids
Ionic liquids
Deep eutectic solvents

a b s t r a c t
The properties and phase equilibria of uid mixtures can have great inuence on chemical product formation and process development. In this work, examples are presented that illustrate the reaction and
separation characteristics of high temperature water, supercritical carbon dioxide, and ionic liquids based
on real-time images made with diamond anvil cells or visual cells. In the formation of ferrosilite from
quartz (SiO2 ) and fayalite (Fe2 SiO4 ), the diffusion of SiO2 to the solid fayalite substrate requires less than
seconds to occur in water at high temperatures due to the enhanced solubility of SiO2 , which has great
technological signicance for developing processes for industrially important luminescent materials. It
is proposed that luminescent materials based on the zinc silicate (Zn2 SiO4 ) family can be made with low
environmental burden. The enhanced solubility of natural products in water at high temperatures allows
for the fractionation of biomass to produce fermentable feedstocks and chemical products as well as for
the efcient separation of natural products. The volumetric properties of n-alkylphenolics with CO2 can
allow for efcient separation from their solid matrix due to viscosity reduction and foaming induced by
changes in pressure. The lack of solubility of ionic liquids in supercritical CO2 allows for biphasic systems that can be used to efciently separate phenolic compounds. Equations of state can provide suitable
correlation. The viscosity reduction provided by solvents such as water, supercritical carbon dioxide, or
organic liquids on ionic liquids allows ionic liquids to be put into a metastable state so that chemical
conversions can occur in ionic liquids below their melting point at room temperature. The physical properties and phase behavior of water and carbon dioxide and mixtures with target compounds are very
important for developing new green chemical processes.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Social expectations for chemical processes that manufacture
products with a minimum of waste and hazardous substances provide us with the opportunity to re-examine the uids, solvents,
and methods being used in industry for the purpose of developing
new processes that are clean, safe, and efcient [1]. The principles of green chemistry [2] and green engineering [3] provide the
foundations for meeting social expectations and embrace the use
of safe methods, nonhazardous chemicals, renewable feedstocks,
atom economy, E-factor [4], and concepts that evaluate product
life cycle and perceived sustainability. The principles of green engineering and green chemistry are conveniently summarized with an
easy to remember mnemonic, IMPROVEMENTS PRODUCTIVELY, in

Corresponding author at: Department of Chemical Engineering, Tohoku University, Aramaki Aza Aoba 6-6-11, Aoba-ku, Sendai 980-8579, Japan.
Tel.: +81 22 795 5863/5864; fax: +81 22 795 5863/5864.
E-mail address: smith@scf.che.tohoku.ac.jp (R.L. Smith Jr.).
0378-3812/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2010.09.030

which the rst Inherently safe and nonhazardous and Minimize

material diversity are important concepts and provide the basic
philosophy for the solvents and processes discussed in this work
[5,6].
Fluids such as air, carbon dioxide, and water can be considered
as some of the most inherently non-hazardous and safe substances
among those that are used in our daily lives and these will most
likely be the working uids of choice for the next generation of
green products and processes due to their compatibility with the
environment. The properties of these uids and conditions for their
application are very important as illustrated in the next few examples.
In automotive transportation, 30 MPa compressed air contained
in carbon-ber reinforced tanks has been proposed as the method
of propulsion for automobiles. Although the carbon footprint of
compressed air vehicles is unfavorable compared with battery electric vehicles, there are clear advantages of compressed air vehicles
in the product life-cycle along with the technological potential
to develop air-engine or pneumatic-combustion hybrid vehicles
[7].

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R.L. Smith Jr., Z. Fang / Fluid Phase Equilibria 302 (2011) 6573

chemical water-splitting cycle [11]. Proposals exist for using high

temperature steam hydrolysis with supercritical CO2 cooling and a
supercritical CO2 power conversion cycle as a method to simplify
the design and improve its energy efciency. Thus, the properties
of water and carbon dioxide will continue to play an important role
in both choosing and implementing the technologies.
In this work, the properties and phase equilibria of uids and
uid mixtures are discussed as they relate to developing green processes. The solubility of quartz in high temperature water provides
the opportunity to develop low-temperature (400600 C) continuous processes high-volume industrial luminescent materials that
are presently produced at high temperatures (>1000 C) and under
batch conditions. Opportunities also exist for using water to efciently process biomass. Supercritical water oxidation for use as a
method to generate energy from biomass is seen as a future green
process. Ionic liquids, which represent highly versatile solvents are
included in the discussion due to their relevance in green chemistry.
The objective of this work is to provide an overview of several topics that have been developed and are under development that take
advantage of the properties of water and carbon dioxide.
2. Water
2.1. Properties and phase equilibria

Fig. 1. Carbon dioxide as a working uid for producing hot water. Water is being
heated from approximately 20 C to 90 C: (a) temperature-entropy diagram for a
water heater based on using carbon dioxide as the working uid; and (b) schematic
of the highly nonlinear heat ux along the axial direction for the tube side of a
single-pass shell-and-tube heat exchanger.

In commercial hot water systems, carbon dioxide is being used

in a transcritical cycle to heat water with a very high coefcient
of performance (COP) as shown conceptually in Fig. 1. Electrical
energy is used to compress the CO2 (Fig. 1,
) to around 10 MPa
and then heat is transferred from the CO2 to the water via a heat
exchanger (Fig. 1,
). In the solvent regeneration, CO2 is throttled into the two-phase region (Fig. 1,
) to around 2 MPa
and then ambient temperature air is used to vaporize the liquid
CO2 . In the cycle, heat transfer to the water (Fig. 1,
) occurs
without phase change over the critical point of CO2 (transcritical) giving the device its high practical efciency. The heat ux
occurring in such heat exchanges is highly nonlinear (Fig. 1b) making usual methods for heat exchanger design based on log mean
temperature differences inapplicable. Therefore, accurate physical
properties and methods of analysis are imperative for these forthcoming devices. The cycle shown in Fig. 1 with CO2 as the working
uid is highly favorable for simultaneous heating and cooling applications in terms of its total equivalent warming impact [8].
In nuclear power applications, the supercritical-water cooled
reactor (SCWR) was considered as one of the possible Generation IV
type reactors, since they are almost 40% more efcient than present
light water reactors (44% versus 3335%) and they have a oncethrough coolant path which allows a reduction in size [9]. The SCWR
has excellent control characteristics since heat is transferred to a
single phase uid and is being developed in Canada and Russia [10].
The very-high temperature reactor (VHTR) system chosen by DOE
for implementation of the Next-Generation Nuclear Plant (NGNP)
uses helium cooling and produces hydrogen through a thermo-

Weingrtner and Franck provide a comprehensive review on

the properties of water including its supercritical state [12]. Some
of the key properties of water include (i) its dissociation equilibria
given by the ion product, Kw = aH+ aOH , (ii) its transport properties,
viscosity, diffusivity, heat capacity and thermal conductivity, (iii) its
dielectric properties given by the relative permittivity, and (iv) its
hydrogen bonding network and solution structure. Temperature
and pressure can be used to vary these properties to selectively
promote desired phenomena for a technological application.
For example, the solubility of quartz, SiO2 , in neutral water at
20 C and atmospheric pressure is approximately 0.0006 wt% [13].
The solubility of SiO2 in water can be calculated over a wide range
of temperatures and pressures with the equation of Fournier and
Potter [13] as shown in Fig. 2. As the temperature of water is varied
at constant pressure, two different trends in the solubility behavior
can be observed.
At a constant pressure that is lower than 100 MPa, the solubility increases and then drastically decreases as the temperature
is increased. At a constant pressure of 23 MPa, the SiO2 solubility
increases to a value of 0.087 wt% at 350 C and drastically decreases
to 0.0081 wt% at 450 C. This retrograde behavior is commonly
observed for many inorganics in water and can be attributed to
the weakening of the hydrogen-bonding network in the supercritical region [14]. The retrograde solubility phenomena of inorganics
in water has been shown to have great technological importance
in materials formation processes [1518] as well as in practical
operation of geothermal energy systems [19].
At a constant pressure that is higher than 100 MPa, the solubility
increases monotonically as the temperature is increased. For example, at 2,000 MPa, the solubility reaches a remarkably high value of
9.07 wt% at a temperature of 800 C. Dissolution and transport of
hydrated silicate species can be extremely rapid as demonstrated
in Section 2.3.
2.2. Experimental methods
Batch, semi-batch and autoclave reactors are the usual method
to initially study many aqueous systems at high temperatures and
pressures. Flow apparatus are used once the reactivities and phase
behavior of the compounds are better understood. Our favorite type

R.L. Smith Jr., Z. Fang / Fluid Phase Equilibria 302 (2011) 6573

67

in a sheet of metal that is held by two opposing diamonds that are

temperature-controlled. Heating of the chamber causes the pressure to increase along an isochore and pressure to increase. Pressure
in the chamber is most conveniently determined by calculation
with an equation of state among the many methods proposed in
the literature. The task of pressure calculation has become much
more convenient with the availability of the ECHO program from
the University of Tbingen [21] that is based on the equations of
Wagner and Pruss [22]. Various types of spectroscopies can be used
with DAC to enhance visual observations.
2.3. Materials
2.3.1. Fayalite
Fayalite (Fe2 SiO4 ) is an important mineral in the Earths magmatic processes [23] and is contained in many metallurgical
intermediates [24]. Under hydrothermal environments, fayalite
will react with quartz to yield ferrosilite (FeSiO3 ) as:
Fe2 SiO4 + SiO2 2FeSiO3

Fig. 2. Solubility of quartz (SiO2 ) in water calculated by the relationship given in Ref.
[13]. Properties of water used in the calculation were from the IAPWS formulation.

of batch reactor is the diamond anvil cell (DAC) because it allows

complete visual observation of the entire cell contents and can used
to study a very wide range of temperatures (200 to 1200 C) and
pressure (0.13000 MPa) easily and safely.
The DAC has been applied to many chemical systems and the
reader is referred to a review written for chemical specialists [20].
The DAC is based on the force (F)area (A) relationship (P = F/A) and
connes a small volume of material (ca. 50 nL) within a chamber

(1)

In water under moderate and neutral conditions, the reaction

might require years or decades to proceed due to the low solubility
of quartz in water, however, at conditions of high temperature and
high pressure, the reaction proceeds on the time scale of seconds.
Fig. 3 shows images of a diamond anvil cell that contains fayalite,
quartz, and water at high temperature (ca. 750 C) and high pressure (ca. 1400 MPa) provided by colleagues at Cornell university
[25]. As the temperature of the solution increases from 752 C to
758 C over a period of 4 s, it can be seen that ferrosilite begins to
crystallize from the solution on the right face of the fayalite crystal.
With a further increase in temperature, the solubility of the quartz
in the water greatly increases as judged by the size of the quartz
crystal and crystallization proceeds rapidly over a period of seconds. The speciation of ferrosilite has been studied in the literature
at lower temperatures [26], but the phase formation mechanism of

Fig. 3. Dissolution of SiO2 in water at high temperatures and pressures and subsequent reaction with fayalite (Fe2 SiO4 ) to form ferrosilite (FeSiO3 ) in a diamond anvil cell
having a nominal chamber diameter of 0.5 mm. Conditions: (a) 0 s, 752.4 C; (b) 2 s, 754.8 C; (c) 4 s, 757.8 C; (d) 15 s, 767.6 C. Images provided as unpublished data of W.B.
Bassett and K. Mibe, Cornell University.

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R.L. Smith Jr., Z. Fang / Fluid Phase Equilibria 302 (2011) 6573

Fig. 4. Dissolution of amorphous SiO2 in water at high temperatures and pressures in a diamond anvil cell having a nominal chamber diameter of 0.5 mm. Conditions: (a)
initial conditions; (b) initial dissolution; (c) homogeneous conditions; (d) precipitation of dissolved SiO2 after cooling showing ne dispersed particles.
Adapted from Ref. [98].

this example is not understood even though the reaction of fayalite

with quartz is well-known in geology.
The example of fayalite reacting with quartz is of interest to
chemical scientists and technologists, because under hydrothermal
conditions it demonstrates that:

materials, they considered zinc oxalate, zinc oxide, manganese (II)

oxalate, and amorphous spherical silica (d = 500 nm). Solubilities
of the raw materials in water were not available and so blank
tests were made in which small amounts of each raw material was
heated with water. For the amorphous silica (Fig. 4), the compound
began to dissolve in water at around 351 C and dissolved com-

(i) rapid dissolution and diffusion of inorganics occurs and

(ii) crystalline silicate materials form at relatively low temperatures
These two points are developed in discussing the formation of
practical materials under hydrothermal and supercritical conditions.
2.3.2. Willemite
Willemite is the geological and historical name for the mineral,
zinc silicate, Zn2 SiO4 . Mn-doped zinc silicate (Zn2 SiO4 :Mn2+ ) is a
practical green phosphor that is produced in large volumes by high
temperature (9001500 C) solid-state reaction paths [27]. In the
solid-state reaction between ZnO, SiO2 and MnCO3 , that occurs
at atmospheric pressure in the presence of various gases at high
temperature, ZnO must diffuse into the SiO2 lattice. The solid-state
reaction is a slow process that requires hours and a considerable
amount of energy to produce material that tends to be nonuniform in nature [27]. Water, under hydrothermal or supercritical
conditions on the other hand, has the potential to allow zinc silicate materials to be produced rapidly and efciently and at much
lower temperatures than the solid-state reaction process due to
its favorable physical properties. The important properties are the
solubilities of the raw materials in the aqueous environment, the
diffusion coefcients of the reacting species, and the solubility of
the product material, all of which can be controlled by temperature
and pressure.
Takesue et al. [28] used a DAC apparatus to examine the phase
formation of Mn-doped zinc silicate in supercritical water. For raw

Fig. 5. Dissolution of zinc oxalate in water at high temperatures and pressures in a

diamond anvil cell having a nominal chamber diameter of 0.5 mm. Conditions: (a)
initial conditions; (b) initial dissolution; (c) formation of polyhedron just after the
observance of needles; (d) cooled sample and conrmation of ZnO by EDX.
Adapted from Ref. [98].

R.L. Smith Jr., Z. Fang / Fluid Phase Equilibria 302 (2011) 6573

69

pletely in water at 417 C and 770 MPa. For the case of zinc oxalate
(Fig. 5), dissolution began at 132 C. Subsequently needle-shaped
particles appeared at 277 C that were probably ZnCO3 and these
grew until 359 C and then transformed into polyhedrons (Fig. 5c).
The cubic-like particles were conrmed to be zinc oxide. For zinc
oxide, heating the compound in water showed no visible change
up to 405 C. Thus, the DAC was very useful in evaluating the phase
behavior of the possible raw materials with water before making
detailed experiments.
Takesue et al. [28] used precursor and achieved homogeneous
nucleation conditions through using the phase conditions studied
in the DAC apparatus and followed the phase transformation with
in situ synchrotron X-ray diffraction [29]. They could conclude that
-zinc silicate could be formed under hydrothermal conditions on
a very short time scale (ca. min). A review on production methods of zinc silicate with critical comparisons of all known methods
has been written and the interested reader is highly encouraged
to access that source [30]. The properties of water, the reaction
environment that it provides, and its phase behavior make it probable that a continuous, low-temperature, and efcient process can
be developed for making industrial phosphors based on the zinc
silicate family.

0.8 wt% is probably still below the solubility limit [37]. The process for this method appears in Fig. 6, which does not address the
recycle of water. The thermodynamic data required for modeling
of the process is considerable although an excellent example does
appear in the literature for the Shell hydrothermal upgrading of
biomass (HTU) process [38]. Nevertheless, the properties of water
and the chemical effects of a small amount of an inorganic salt
allow a homogeneous solution to be formed with woody biomass
slurries and therefore the development of green processes for the
conversion of biomass are feasible.

2.4. Biomass resource conversion

6nCO + 6nH2 O 6nH2 + 6nCO2

2.4.1. Water soluble compounds

Willow is a woody crop that has the potential to be used as a local
source of biomass for heat, electricity, and chemicals because it is
fast growing in cooler regions such as the Tohoku region of Japan
[31]. Conversion of willow by enzymatic hydrolysis is inhibited by
the presence of lignocellulose, whereas acid hydrolysis is process
and energy intensive and severely degrades the glucose produced.
Hot water, on the other hand, provides an alternative method that
does not require acids or harsh additives to hydrolyze the material. A comprehensive overview of the hydrolysis of biomass via
hydrothermal methods is given by Yu et al. [32].
Hashaikeh et al. [33] studied the hydrothermal dissolution of
willow with batch, DAC, and ow type experiments. The DAC was
used to determine the qualitative phase behavior of the system
where it was found that heat rates of greater than 5 C/s were
needed to give dissolution of the material in water but invariably recondensation of oligomers occurred that prevented ow operation
at temperatures higher than 300 C. Thus, short reaction times with
higher heating rates would seem to be needed for a homogeneous
phase.
The use of alkali salts has been studied for some years in the
liquefaction of biomass [34,35]. Fang and Fang [36] used DAC experiments with willow and considered the use of dilute alkali solutions
to completely solubilize the material. Willow, Na2 CO3 and water
were loaded into the DAC chamber. Then, studies were made where
it was found that willow could be completely dissolved with little or no residue at 330 C by using heating rates of at least 8 C/s
and very low concentrations of Na2 CO3 of 0.8 wt%. The solubility of
Na2 CO3 in water decreases with increasing temperature, but still

Fig. 6. Proposed process for production of water soluble compounds from woody
crops.
Adapted from Ref. [34].

2.4.2. Hydrogen
Biomass can be considered as a mixture of cellulose (C6 sugars),
hemicellulose (C5 sugars) and lignin (polyphenolics) compounds.
Instead of converting biomass to chemicals as in the previous section, it is possible to produce hydrogen and methane for use in other
processes. The amount of hydrogen that can be produced from the
perfect hydrolysis of cellulose (Eq. (2)) based on a compound that
contains n moles of glucose is:
(C6 H10 O5 )n + nH2 O nC6 H12 O6 perfect cellulose hydrolysis

(2)

nC6 H12 O6 6nH2 + 6nCO

(3)

perfect

glucose

gasication

water-gas shift reaction

(C6 H10 O5 )n + 7nH2 O 12nH2 + 6nCO2

(4)
(5)

For n moles of glucose and its perfect gasication (Eq. (3)), and
through the water-gas shift reaction (Eq. (4)), it is possible to obtain
12 moles of hydrogen for every mole of glucose according to Eq. (5).
For the case of hemicellulose represented by (C5 H8 O4 )n , 10 moles
of hydrogen are possible to be produced for every mole of xylose
(C5 H10 O5 ). For the case of lignin that can be represented as an intermediate monomeric alkylphenolic species, (C10 H10 O3 )n [39], the
amount of hydrogen that can be produced from n moles
(C10 H10 O3 )n +nH2 OnC10 H12 O4

perfect lignin hydrolysis

(6)

nC10 H12 O4 + 6nH2 O 12nH2 + 10nCO

perfect steam reforming

(7)

10nCO + 10nH2 O 10nH2 + 10nCO2 water-gas shift reaction (8)

(C10 H10 O3 )n + 17nH2 O 22nH2 + 10nCO2

(9)

For n moles of an alkylphenolic, for perfect hydrolysis and steam

reforming, Eqs. (6) and (7), it is theoretically possible to produce 22
moles of hydrogen for every mole of alkylphenolic according to Eq.
(9). In both the gasication of cellulose and lignin, the water-gas
shift reaction is an important source of hydrogen [40].
Fang et al. [41] studied cellulose and Na2 CO3 additive with and
without Ni catalyst with DAC, batch and ow experiments. The DAC
was helpful for not only observing the conditions where the mixtures became homogeneous, but also for knowing the conditions
where gas was formed and the physical interaction of the solution
with the catalyst. In another work, the effect of catalysts (Ni, Ru, Pt)
on the phase behavior of cellulose + water and glucose + water mixtures was considered [42]. The Pt catalyst was found to promote a
homogeneous and light colored phase in the trials with glucose and
the ow experiment gave a 40 mol% H2 gas stream, thus conrming the importance of the phase observations in the DAC apparatus
[42]. A catalytic reactor instead of the bio-reactor shown in Fig. 6
was proposed in that work to produce hydrogen.
Considerable effort has been devoted to the noncatalytic [39,43]
and catalytic methods [44,45] to gasify biomass in water and several helpful reviews are available [4649]. Both the phase behavior
of the reactants and products with water and the selection of catalysts are important in developing future green processes.

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R.L. Smith Jr., Z. Fang / Fluid Phase Equilibria 302 (2011) 6573

Fig. 7. Temperature prole of a biomass boiler for which spent tea leaves are heated in a hydrothermal environment. After air is added to the mixture, an auto-thermal effect
can be seen (left) and the efuent changes greatly for the case of with air (top) and without air (bottom).

2.4.3. Energy
An integrated gasication combined cycle (IGCC) combusts slurried coal with air or oxygen at high temperatures and produces
syngas (CO + H2 ). Excess heat from combustion is combined with
a gas turbine to produce electricity. The syngas can also be combusted and used to generate electricity. IGCC facilities are beginning
to supplement their feeds with up to 30% biomass. Biomass integrated gasication combined cycles (BIGCC) use biomass instead
of coal and often use uidized beds and operate at low pressures.
They are not realized yet, but they are being considered as add-on
facilities such as those for sugarcane [50], paper or ethanol [51].
In previous research, Arai et al. [52] proposed that supercritical water oxidation technology could be used to efciently convert
biomass into energy. In that proposal [52], the adiabatic ame
temperature was calculated for cellulose and water mixtures with
stoichiometric oxygen at pressures up to 30 MPa. At pressures
above about 20 MPa, the combustion becomes spontaneous and
can be sustained. A ow sheet and apparatus have been developed
based on semi-batch operation. Fig. 7 shows some initial results
for the case of a biomass feedstock of spent tea leaves that are oxidized with air. For the case of no air, water is brown and turbid as
might be expected. However, for the case of with air, the efuent
is clear and changes color to become completely transparent. The
auto-thermal effect can be clearly seen in the gure beginning at
about 17 min run time. The process, when realized, will be able to
convert biomass into energy with high efciency. In achieving complete oxidation in the biomass boiler, the phase behavior and the
stream mixing are very important along with the heat transfer that
occurs. Estimation methods for the properties and phase behavior
as the oxidation proceeds are needed to realize the process.
3. Carbon dioxide
Supercritical carbon dioxide (scCO2 ) is widely used in applications associated with extractions [53], separations [54], materials
[55], polymer syntheses [56], polymer processing [57], chromatog-

raphy [58], ionic liquids [59] and reactions [60]. Specialized reviews
are available [6171] and a comprehensive compilation of the solubilities of more than 780 solutes in supercritical carbon dioxide
has been published [72]. Several applications will be discussed in
this section to highlight the properties of scCO2 .
3.1. Mass separating agent
Lipids found in natural products are usually conned within
membranes or within a solid matrix. In the processing of oilcontaining materials, scCO2 can be used as a non-reactive solute
to decrease the time required to separate an oil from a solid matrix
via volume expansion, viscosity reduction or both of these effects.
The use of pressure swing enhances the efciency of separation
by disrupting membranes and promoting oil-scCO2 phase contact.
The technique has been applied to cashew nut shell liquid [73,74],
herbs [75,76], palm kernel oil [77], canola [78], and sh oil [79]
with good results. For the case of cashew nut shell liquid (CNSL)
[73], the temperature can be used in addition to the pressure to
promote the separation as shown in Fig. 8. As shown in Fig. 8, CNSL
bubbles when reducing the pressure at 20 C under conditions of
3 phases. At temperatures higher than the critical temperature of
CO2 , CNSL also bubbles when reducing the pressure thus providing a mechanism for separating the oil from the solid matrix. Such
a method is greatly needed in the general processing of cashew,
not only for industrial efciency but more importantly, for human
health [80].
3.2. Biphasic system
Carbon dioxide generally forms two phases with ionic liquids,
which makes it convenient for both separations and reactions.
On the other hand, scCO2 can be made to dissolve considerable
amounts of an ionic liquid into the supercritical phase by addition
of a third component [81], or to cause a solute to crystallize from
the ionic liquid phase [82] or even to be made homogeneous in a

R.L. Smith Jr., Z. Fang / Fluid Phase Equilibria 302 (2011) 6573

71

25
benzene-benzyl alcohol
benzene-naphthalene
benzene-chlorobenzene
benzene-toluene

separation factor [-]

20

15

10

10

12

14

16

18

20

P [MPa]
Fig. 9. Separation factors calculated with the SanchezLacombe equation of state
for [bmim][PF6 ]CO2 at 60 C.

Fig. 8. Phase behavior of carbon dioxide with cashew nut shell liquid (CNSL) adapted
from Ref. [71]. Visual appearance of oil during pressure changes for CNSL-CO2 only
and for CNSL contained in the solid matrix (top). Phase behavior of CNSL-CO2 calculated with the PengRobinson equation of state.

ternary system under the proper conditions [83]. In this section,

biphasic ionic liquidscCO2 systems are discussed.
3.2.1. Partition coefcient
The partitioning of organic solutes between an ionic liquid phase
and a scCO2 phase is of interest for many separation and reaction processes. Basic data are being measured by several groups
[8488]. Application of theory to either predict or correlate the
data use methods such as linear solvation energy relationships
(LSER) that provide qualitative information [85], semi-empirical
models such as equations of state [89,90] that provide quantitative correlation and limited prediction, and quantum chemistry
based models COSMO-RS [91] that provide quantitative predictions with detailed information on the molecular interactions. In
this work, the SanchezLacombe equation is discussed since it is
widely applicable to both polymer and ionic liquid systems.
In the partitioning of a solute between a supercritical CO2 phase
(scCO2 phase) and an ionic liquid phase (IL phase), a weight ratio
separation factor can be dened as:
=

KwA

(10)

KwB

IL phase

IL phase

(= w scCO2 phase /w
(= w scCO2 phase /w
) and KwB
)
where KwA
B
B
A
A
are the weight ratio based partition coefcients of solute A and
solute B, respectively. Once sufcient data have been measured and
correlated, it is possible to use an equation of state to predict the
separation factors.
Fig. 9 shows calculations of the separation factors as determined
from the SanchezLacombe equation of state for aromatic solutes
in the [bmim][PF6]scCO2 biphasic system [92]. As shown in Fig. 9,
separation factors have values as high as 20 and these decrease
with increasing pressure. The equation of state can also be used to
examine the variation of the separation factors with temperature.
In the SanchezLacombe equation, the interaction energy, *,
is considered to be a constant and does not depend on tempera-

ture. As the temperature of a system changes, it is clear that both

Coulombic interactions and hydrogen-bond interactions do depend
on temperature. Machida et al. [93] recently proposed the following simple function that greatly improves the representation of the
pressurevolumetemperature behavior of pure uids including
ionic liquids:
(T ) = 0

T
1 + T

(11)

where 0 is the asymptotic value of the interaction energy at the

high temperature limit given by the original equation and a is a
constant that depends on the interaction energies. For many substances, 1/ can be considered to be a constant or as a linear
function of the magnitude of the interaction energies (Fig. 10). The
application of Eq. (11) to mixtures is presently being examined and
should provide some insight into the trends of available separation
factors. The development of equations of state for scCO2 ionic liquid systems is an ongoing research topic and many developments
can be expected in the future.
4. New processes on the horizon
Many new processes that use the principles of green engineering and green chemistry are on the horizon. The foundations of
the processes depend on the reliability of the properties and phase
behavior of chemical systems. Many new energy systems will be
built with water or carbon dioxide as the working uids and continued development of thermophysical property formulations for
these and other working uids is needed.
Low-temperature processes for practical industrial luminescent
materials have cleared many of the technical hurdles and will begin
to be adopted by industry. Demonstration of continuous production
of the zinc silicate family of industrial phosphors is being published
that provides appropriate sources of silica [94].
Efcient ways to either liquefy or gasify biomass are available
and it is likely that many new chemical processes based on selected
feedstocks will be developed. The biomass boiler has been demonstrated for conversion of waste biomass to energy with emphasis
on the local scale. Detailed trials will be published on various feedstocks such as spent tea or spent coffee grinds.

72

R.L. Smith Jr., Z. Fang / Fluid Phase Equilibria 302 (2011) 6573

Many physical properties and phase equilibria studies are still

needed to understand the simplest of examples outlined in this
work. Through sharing of methods and technologies between
research elds, progress developing green processes can be greatly
accelerated.

700
650
600

1/ [K]

550
500

Acknowledgements

450

The authors wish to acknowledge partial nancial support of

the Education Global Center of Excellence (Global COE) and the
Ministry of Education, Science, Sports and Culture (RLS) and the
partial nancial support of the Chinese Academy of Sciences (ZF)
for support of this research.

400
350
300
250

References

200
150

1/ = 0.10070 423.9

100
50
0
5000

6000

7000

8000

9000

10000

11000

12000

0 [kJ/mol]
Fig. 10. Correlation of the temperature dependence of interaction energies in the
SanchezLacombe equation of state as a function of the magnitude of the interaction
energies.
Adapted from Ref. [91].

Hydrothermal ames, in which an organic is oxidized in the

presence of water, have been studied in the past as an efcient
method for waste treatment. In the development of new drilling
technologies, hydrothermal ames are being evaluated as a new
thermal spallation drilling technology [95]. Such technology has
application not only as a clean and efcient method for drilling but
also as a form of in situ petroleum upgrading.
Water is seen as a method for upgrading and extending present
petroleum reserves [96]. Bitumen upgrading with water is an active
topic and water acts as a solvent for reducing coke formation during
the upgrading process. Key to the process is the phase behavior of
highly complex and undened polyaromatic compounds and maintaining the homogeneity of the system as the reaction progresses.
Many possible separation and reaction processes are being proposed and coming online for carbon dioxide. Biphasic reactions
and separations with supercritical CO2 are attractive. There are
new opportunities for using ionic liquids in their metastable liquid
state. For example, the melting point of the ionic liquid [bmim][Cl]
is about 70 C. However, if liqueed by heating above its melting
point, it can be made to dissolve solids such as fructose. Addition
of scCO2 or organic solvents to reduce the viscosity allows the catalytic conversion of fructose to 5-hydroxymethylfurfural to occur at
high efciency at close to ambient temperatures due to the viscosity
reduction provided by the added solvent or scCO2 [97].
5. Conclusions
Physical properties and phase behavior of uids and uid
mixtures can be used to develop many environmentally friendly
chemical processes. Air, water and carbon dioxide will be used as
the working uids in many future devices and processes. As we continue to explore the properties of these uids and uid mixtures,
it is inevitable that there will be some discoveries that will lead to
new practical processes.

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