J.

of Supercritical Fluids 52 (2010) 113–124

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids

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

Continuous salt precipitation and separation from supercritical water. Part 2.

Type 2 salts and mixtures of two salts
Martin Schubert, Johann W. Regler, Frédéric Vogel ∗
Paul Scherrer Institut, Laboratory for Energy and Materials Cycles, CH-5232 Villigen PSI, Switzerland

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

Article history: Using a continuously operated laboratory plant for the catalytic hydrothermal gasification of biomass
Received 20 July 2009 featuring a supercritical water salt separator we investigated the separation performance of three dif-
Received in revised form 6 October 2009 ferent binary type 2 salt–water mixtures and three ternary salt–water mixtures that consisted either of
Accepted 7 October 2009
two type 1 salts or two type 2 salts dissolved in water. It turned out that a concentrated salt brine could
not be recovered at the salt separator for the binary type 2 salt–water mixtures of Na2 CO3 , Na2 SO4 , and
Keywords:
K2 SO4 . These salts precipitate as solids from supercritical water and thus lead to salt deposits inside the
Supercritical water
salt separator vessel.
Salt separation
Type 1 salt
The ternary mixtures of two type 1 salts dissolved in water (KH2 PO4 –K2 HPO4 –H2 O and three different
Type 2 salt mixtures of NaNO3 –K2 CO3 –water) exhibited a separation performance similar to the binary solutions
Hydrothermal gasification of type 1 salts that were discussed in Part 1 of this article. However, the mixtures showed separation
Salt mixtures performances that were different from the corresponding single salt solutions.
It was also possible to recover a concentrated brine when feeding solutions containing the two type
2 salts Na2 CO3 and K2 SO4 . For these mixtures a certain amount of the type 1 salt K2 CO3 might form in
supercritical water leading to salt separation efficiencies up to 95% for these mixtures.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction of the more common approaches. Salt precipitation inside a super-

The catalytic hydrothermal gasification in near or supercritical
water is an efficient technique for the conversion of waste biomass
streams into clean biofuels [1–3]. We demonstrated up to 99% gasi-
fication of slurries containing up to 30 wt.% wood, 10 wt.% micro
algae, or a mixture of organic compounds to mainly CH4 , CO2 , and
H2 [4–7]. However, salts contained in the biomass such as sulfates
were found to poison the catalyst and have therefore to be removed
before the reaction mixture enters the catalytic reactor [5,8].
As complete removal of the salts can only be achieved after the
break-up of the cells and liquefaction of the organic biopolymers,
the salt separation needs to be carried out under hydrothermal con-
ditions. Several separation techniques have been described that
take advantage of the dramatic change of the solvent properties
of water near the (pseudo-) critical point1 [9,10]. In our process
development plant [11], a reverse-flow vessel is used to precipi-
tate the salts from the supercritical reaction mixture, which is one
∗ Corresponding author. Tel.: +41 56 310 2135; fax: +41 56 310 2199.
E-mail address: Frederic.vogel@psi.ch (F. Vogel).
1
The critical point of water is at a temperature of Tc = 374 ◦ C and at a pressure of
pc = 22.1 MPa. Commonly, the term “supercritical” refers to water above Tc and pc .
At a given pressure above pc the pseudo-critical temperature Tpc is the temperature
at which water exhibits a maximum in the specific isobaric heat capacity.
critical water salt separator was studied at the macroscopic scale in
our group by in situ neutron radiography [12,13]. We learned that a
solution of Na2 SO4 will plug the separator but that certain mixtures
of Na2 SO4 and Na2 B4 O7 , or mixtures of Na2 SO4 and K3 PO4 can be
precipitated without plugging. The addition of phosphate salts to
a hydrothermal process was indeed suggested to prevent plugging
[14]. These phenomena can be related to the nature of the salts in
the mixture. Under supercritical conditions, a certain temperature
and pressure range exists where dilute solutions of a type 1 salt,
such as K3 PO4 or Na2 B4 O7 , form a liquid and a vapor phase, each
saturated with salt, with the liquid phase containing more salt than
the vapor phase; dilute solutions of a type 2 salt, such as Na2 SO4 ,
form a supercritical fluid phase and a solid salt phase [9,15,16]. Pre-
cipitation of solid Na2 SO4 from a 4 wt.% solution at 25 MPa on a hot
finger was shown by Hodes et al. [17]. Sodium sulfate precipitation
at around 400–430 ◦ C and 25 MPa on the reactor walls in the non-
transpiring part of a supercritical water oxidation transpiring-wall
reactor was observed by Príkopský [18] when processing artifi-
cial waste water, i.e. a mixture of 6 wt.% methanol containing up
to 3 wt.% Na2 SO4 . Rogak and Teshima [19] developed a heat- and
mass-transfer model to predict the sodium sulfate deposition rate
within a tubular reactor at 25 MPa and temperatures around 385 ◦ C
with reasonable agreement with the experimental data.
In order to study the separation performance of different salts
and salt mixtures, we investigated the salt separation of several salt

0896-8446/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2009.10.003
114 M. Schubert et al. / J. of Supercritical Fluids 52 (2010) 113–124

Table 1
Binary and ternary water and salt mixtures investigated in this work.

Binary water and salt mixtures (one salt dissolved in water) Ternary water and salt mixtures (two salts dissolved in water)
a,b a,c
Type 1 salts Type 2 salts Type 1–type 1c Type 2–type 2c , d

K3 PO4 , K2 HPO4 , KH2 PO4 KH2 PO4 –K2 HPO4

NaNO3 , KNO3 , Ca(NO3 )2 NaNO3 –K2 CO3 d
K2 CO3 , KHCO3 , (NH4 )2 CO3 Na2 CO3
NaCl, KCl, NH4 Cl K2 SO4 –Na2 CO3
(NH4 )2 SO4 Na2 SO4 , K2 SO4
a
For an overview of the classification of the salts see [16,23].
b
Discussed in Part 1 of this article [11].
c
Discussed in this part.
d
Note that this mixture could also be classified as type 1–type 2, as a permutation of the ions leads to the mixture KNO3 –Na2 CO3 and K2 CO3 –Na2 SO4 , respectively.

solutions containing either a type 1 or a type 2 salt or a mixture of
two type 1 or two type 2 salts. All water–salt mixtures and their
classification into type 1 and type 2 investigated in this work are
summarized in Table 1. The separation performance of solutions
containing only one type 1 salt was discussed in Part 1 of this article
[11]. Salt separation and the recovery of a concentrated brine with
high efficiencies was possible for all of those solutions.
In this paper we present the results obtained with different solu-
tions containing one of the type 2 salts Na2 SO4 , K2 SO4 , or Na2 CO3 , or
mixtures of either two type 1 (KH2 PO4 –K2 HPO4 or NaNO3 –K2 CO3 )
or two type 2 salts (K2 SO4 –Na2 CO3 ).
2. Experimental
2.1. Salt separation experiments—general procedure
The salt separation experiments were carried out using the con-
tinuously operated laboratory plant described in detail in Part 1 of
this article [11].
For all experiments, a pressure of 30 ± 0.5 MPa was maintained
and the temperature of the pre-heater was set to 300 ◦ C, result-
ing in a fluid temperature of about 280 ◦ C at the pre-heater exit.
Other experimental parameters are given in Tables 2 and 3. For each
experiment the fluid temperature within the salt separator was
increased stepwise from subcritical to supercritical. The applied
temperature steps are given in Table 4. The chemicals used in this
study are listed in Table S1 of the supplementary materials. A more
detailed description of the general experimental procedure may be
found in Part 1 of this article [11].
2.2. Sample analyses and data evaluation
Elemental analysis of the aqueous samples containing either Na,
K, or P was carried out with a Liberty 110 ICP-OES spectrometer
(Varian) with argon as carrier gas.
Ion chromatography was used to measure sulfate and nitrate
in the samples. The chromatograph was an HPLC Summit sys-
tem (Dionex) equipped with a Metrosep A Supp 5 analytical anion
separation column (Metrohm) and an ASRS 300 anion suppressor
(Dionex). Detection was performed with an ED 50 electrochemical
detector (Dionex) in the conductivity mode.
For measuring the inorganic carbon (carbonate and bicarbonate)
content, an IL530 TOC-TIC-TN analyzer (Hach) and a vario TOC cube
(Elementar) were used.
All samples were diluted with deionized water to match the cal-
ibrated range of each analytical method. The diluted samples were
filtered using a PTFE filter (pore size 0.45 ␮m) before ion chromato-
graphic analysis. More detailed information on the setting of the
analytical methods devices may be found in Part 1 of this article
[11].
In each experiment, for each ion of the salt investigated, its
recovery in the salt separator/brine effluent (the separation effi-
ciency), in the reactor effluent (the remaining fraction) and the
overall ion recovery were calculated. As only the individual ions of
the salts can be detected, all salt recoveries are actually determined
as recoveries of the individual ions. This data evaluation followed
exactly the evaluation method described in Part 1 of this article
[11].
The relative error for the salt/ion concentration measurements
was estimated to be 2.4%. For the mass flow rates, the standard
deviation from the scale signals was taken as an estimate of the
absolute error of these flow rates (see Tables 2 and 3).
For the temperatures T4, T5 and T15 listed in Table 4, the stan-
dard deviation was always less than 1 ◦ C; however, 1 ◦ C was the
maximum deviation in some cases. The deviations of the fluid tem-
peratures T13 and T16 of temperature code I in Table 4 are the
standard deviations of the respective fluid temperatures at steady
state for each temperature setpoint. For the temperature code II,
the steady state mean fluid temperatures at position T13 and T16
of the experiments U–Z are listed in Table 4. The uncertainty listed
together with the mean value reflects the variation observed for
the different experiments at the same setpoint. The fluid temper-
ature at T13 is different from the values listed in Table 4 for the
experiments Q–S (see Fig. 2). However, if referring to an individual

Table 2
Parameters for the salt separation experiments with mixtures of a type 2 salt and water.

Exp. Salt Feed parameters Effluent parameters Total mass balance closure (%) Temperature codec
−3 a b b b
cSalt (10 mol/L) ṁFeed (g/min) ṁS (g/min) ṁR (g/min)

Q Na2 CO3 102 ± 2 17.0 ± 0.3 2.5 ± 0.1 14.6 ± 0.3 100 ± 4 II
R K2 SO4 84 ± 2 16.5 ± 0.6 2.5 ± 0.1 14.0 ± 0.6 100 ± 8 II
S Na2 SO4 100 ± 2 16.1 ± 0.3 2.5 ± 0.1 13.6 ± 0.3 100 ± 6 II
a
Salt concentration of the feed determined from ICP-OES analysis of the cations of the respective salt at 25 ◦ C and 0.1 MPa, referred to as concentration per molecular
formula, e.g. 50 mmol/L K2 SO4 contains 100 mmol/L K+ and 50 mmol/L SO4 2− .
b
The symbols ṁFeed , ṁS and ṁR represent the mass flow rate of the feed, the salt separator effluent and the reactor effluent, respectively.
c
Temperature setpoints of the salt separator, compare Table 4.
 M. Schubert et al. / J. of Supercritical Fluids 52 (2010) 113–124 115

Table 3
Parameters for the salt separation experiments with ternary mixtures (two salts in water). Experiments T–W: both salts are type 1 salts. Experiments X–Z: both salts are
type 2 salts.

Exp. Salt 1 Salt 2 Feed parameters Effluent parameters Total mass balance Temperature
closure (%) codec

cSalt 1 cSalt 2 cSalt 1 /cSalt 2 ṁFeed ṁS ṁR

(10−3 mol/L)a (10−3 mol/L)a (g/min)b (g/min)b (g/min)b

T KH2 PO4 K2 HPO4 98d 2.3d 42.5 16.8 ± 0.6 2.6 ± 0.1 14.2 ± 0.6 100 ± 8 I
U NaNO3 K2 CO3 103 ± 3 51 ± 1 2.0 16.2 ± 0.3 2.6 ± 0.1 13.7 ± 0.3 100 ± 4 II
V NaNO3 K2 CO3 47 ± 1 48 ± 1 1.0 16.0 ± 0.3 2.5 ± 0.1 13.4 ± 0.3 100 ± 4 II
W NaNO3 K2 CO3 55 ± 1 120 ± 3 0.5 16.3 ± 0.5 2.6 ± 0.1 13.7 ± 0.4 100 ± 6 II
X K2 SO4 Na2 CO3 50 ± 1 50 ± 1 1.0 15.8 ± 0.4 2.6 ± 0.1 13.2 ± 0.3 100 ± 5 II
Y K2 SO4 Na2 CO3 40 ± 1 58 ± 1 0.7 15.8 ± 0.5 2.6 ± 0.1 13.2 ± 0.5 100 ± 7e II
Z K2 SO4 Na2 CO3 59 ± 1 37 ± 1 1.6 15.9 ± 0.5 2.6 ± 0.2 13.3 ± 0.4 100 ± 7 II
a
Salt concentration of the feed determined from ICP-OES analysis of the cations of the respective salt at 25 ◦ C and 0.1 MPa, referred to as concentration per molecular
formula, e.g. 50 mmol/L K2 SO4 contains 100 mmol/L K+ and 50 mmol/L SO4 2− .
b
The symbols ṁFeed , ṁS and ṁR represent the mass flow rate of the feed, the salt separator effluent and the reactor effluent, respectively.
c
Temperature setpoints of the salt separator, compare Table 4.
d
Nominal concentration of the feed solution. The ratio of KH2 PO4 to K2 HPO4 was chosen to maintain a pH of 5.5. The actual measured salt concentration of potassium and
phosphorus was 97.1 ± 2.3 and 98.3 ± 2.4 mmol/L, respectively.
e
There was a small leak at the dip tube entrance of the salt separator for the 500 ◦ C setpoint. Thus the mass balance was below 100% for this setpoint (compare overall ion
recoveries in Tables S4 and S5 of the supplementary materials).

experiment carried out with temperature code II the text refers to
individual fluid temperatures of the respective experiment.
3. Results and discussion
3.1. Comparison of the separation performance of single type 1
and type 2 salts
Before investigating the separation performance of salts from
mixtures, the separation performance of each salt in such a mix-
ture should be investigated in a binary mixture (one salt dissolved
in water) first. As Part 1 of this article [11] deals with the salt
separation performance of various type 1 salts, the separation per-
formance of three type 2 salts, i.e. Na2 CO3 , Na2 SO4 , and K2 SO4
compared to that of type 1 salts, is described in this section.
These three type 2 salts exhibited a similar separation per-
formance. As an example, the evolution of the conductivities of
the effluents normalized to the respective feed solution, the sep-
aration efficiency, and the remaining salt fraction in the reactor
effluent of the cations of the experiments Q–S are depicted in
Fig. 1a and b. The overall recoveries of all type 2 salts investigated
are given in Tables S2 and S3 of the supplementary materials. For
Na2 CO3 and subcritical fluid temperatures in the hot part of the
salt separator (390 ◦ C separator setpoint temperature) the conduc-
tivities and thus the concentration of the effluents reached nearly
the value of the feed solution, resulting in a good overall recov-
ery. No explanation can be given for the recovery of around 130%
in experiment R (K2 SO4 ). The lower overall recovery of 87% for
Na2 SO4 may be explained by some salt precipitation in the hot-
ter lower parts of the salt separator vessel (compare temperature
profiles of the salt separator given in Part 1 of this article [11]),
where the solubility of Na2 SO4 was reached. Increasing the salt
separator temperature led to a decrease of the salt concentration
below the concentration of the feed in both effluents. This can be
explained by a buildup of solid salt in the hot zone of the salt sep-
arator (all other parts of the experimental rig were subcritical),
further confirmed by the poor overall recoveries. Probably the type
2 salts precipitated at the salt separator wall because the wall is
the hottest part, as the salt separator is heated externally. Precip-
itation of Na2 SO4 from a 4 wt.% sodium sulfate solution on a “hot
finger” at 25 MPa and 356 ◦ C fluid temperature (the temperature
of the “hot finger” surface was around 380 ◦ C) was observed by
Hodes et al. [17]. A buildup of sodium sulfate within a supercriti-
cal water salt separator, similar to the one used in this study, was
recently observed by Peterson et al. [12] using neutron radiogra-
phy. In addition, after a preliminary experiment that we carried
out before this study we found a solid salt plug of Na2 SO4 inside the
salt separator with the same inner diameter as the vessel and about
17 cm long. In that experiment the system was rapidly depressur-
ized to “quench” the plug by removing the water as vapor and
preventing re-dissolution of the plug, after having fed a 1 wt.%
Na2 SO4 solution for about 5 h. The plug covered more than half
of the length of the lower heated zone and ended roughly where
the lower heated zone ended. Below that point the tube was blank.
Above the salt plug the separator tube was covered with a thin salt
layer.

Table 4
Fluid temperatures within the salt separator for different vessel setpoints at steady state. For an explanation of the temperature deviations, see text.

Temperature code Vessel setpoint Heating block temperatures Vessel outer wall temperature Fluid temperatures

TSep (◦ C) T4 and T5a (◦ C) T15a (◦ C) T13a , b (◦ C) T16a (◦ C)

410 410 ± 1 409 ± 1 366 ± 2 183 ± 1

420 420 ± 1 419 ± 1 376 ± 2 191 ± 1
430 430 ± 1 429 ± 1 388 ± 1 201 ± 1
I
440 440 ± 1 439 ± 1 398 ± 1 208 ± 2
450 450 ± 1 449 ± 1 403 ± 1 218 ± 2
460 460 ± 1 459 ± 1 406 ± 1 223 ± 1

390 390 ± 1 389 ± 1 342 ± 1 185 ± 2

430 430 ± 1 429 ± 1 381 ± 5 215 ± 2
II
470 470 ± 1 469 ± 1 407 ± 1 246 ± 2
500 500 ± 1 499 ± 1 417 ± 1 264 ± 1
a
Compare Fig. 1 in Part 1 of this article [11].
b
Note that the fluid temperatures at position T13 are meaningful for experiments U–Z only.
116 M. Schubert et al. / J. of Supercritical Fluids 52 (2010) 113–124
Fig. 1. (a) Electrical conductivities of the effluents of the salt separation experiments
of Na2 CO3 (exp. Q), K2 SO4 (exp. R) and Na2 SO4 (exp. S) normalized to the electrical
conductivity of the respective feed solution. A steady state with respect to constant
conductivities of the effluents stream was only achieved for 390 ◦ C salt separator
setpoint. (b) Salt separation efficiencies and remaining salt fraction in the reactor
effluent of the cations of experiments Q–S.
As an example for all experiments carried out with a binary type
2 salt mixture, the hot fluid temperature at position T13 at differ-
ent temperature setpoints of the salt separator for experiment Q
(Na2 CO3 ) is depicted in Fig. 2. For comparison, the hot fluid tem-
perature of the salt separator for a type 1 salt is included in that
figure as well. A buildup of salt in the salt separator might have led
to a decreased heat transfer from the wall to the fluid due to an
insulating salt layer. Additionally, a salt plug might inhibit the mix-
ing of the hot fluid from the lower part of the salt separator with the
colder fluid at the top entrance (refer to the temperature profiles
of the salt separator in Part 1 of this article [11]), as suggested by
Peterson et al. [13]. For the type 2 salts, when increasing the salt
separator temperature to the next setpoint the fluid temperature
increased at first but then started to decrease to a certain value.
This phenomenon may be explained as follows: upon increasing
the fluid temperature more salt precipitated, leading to a decrease
Fig. 2. Comparison of the temperature of the hot fluid inside the salt separator
vessel during a salt separation experiment of a type 1 (experiment J) and a type 2
salt (experiment Q; temperature at position T13, compare Fig. 2 in Part 1 of this
article [11]).
of the conductivity in the reactor effluent. The buildup of precipi-
tated type 2 salts, known to be “sticky”, would deteriorate the heat
transfer from the wall to the fluid, decreasing the fluid tempera-
ture at position T13 (see Fig. 2). As the fluid temperature decreased
again, more salt remained dissolved leading to an increase of the
conductivity in the reactor effluent. An inhibition of the mixing of
the hot fluid from the lower part of the vessel with the colder fluid
at the top entrance would lead to the same phenomenon. It is likely
that there is a superposition of both effects. However, this was not
observed for the type 1 salts. For the type 1 salts a steady state for
the fluid temperatures and the effluent conductivities was always
reached (refer also to Part 1 of this article [11]).
Khan and Rogak [20] reported the following empirical solubility
relationships for Na2 CO3 and Na2 SO4 in a binary water and salt
mixture:
• For Na2 CO3 :
log[CNa2 CO3 ] = 6.24 × 10−8 × 3 − 8.48 × 10−5 × 2
+0.046 ×  − 9.74 (1)
• For Na2 SO4 :
log[CNa2 SO4 ] = −2.16 × 10−5 × 2 + 0.037 ×  − 13.11 (2)
where log[Ci ] is the natural logarithm of the salt solubility C (wt.%),
and  (kg/m3 ) is the fluid density (density of pure water) at a given
temperature and pressure. A comparison of the measured salt con-
centrations of both effluents of the experiments with Na2 CO3 and
Na2 SO4 with the solubility relationships of Khan and Rogak is given
in Table 5. The solubility Scalc. of the respective salt is calculated at
the measured fluid temperature T13 and the corresponding fluid
density at 30 MPa [21]. The measured concentrations of both salts is
always well (in the reactor effluent) or far below (in the brine efflu-
ent) the calculated solubility that would have been expected from
the fluid density corresponding to the fluid temperature at position
T13. The salt concentration was much lower in the brine effluent
at the salt separator temperature setpoints of 430–500 ◦ C. This can
be explained by a higher fluid temperature downstream in the salt
separator, as illustrated by the axial temperature profiles in Part 1
of this article [11]. This is also supported by the temperature values
given in the last two columns of Table 5. These temperatures cor-
 M. Schubert et al. / J. of Supercritical Fluids 52 (2010) 113–124 117

Table 5
Comparison of the effluent salt concentration of Na2 CO3 and Na2 SO4 with the solubility model for both salts from the literature [20].

TSep (◦ C) T13a (◦ C) Densityb (g/mL) Effluent conc.c (wt.%) Scalc. d (wt.%) TBrine Effl. e (◦ C) TReact Effl. e (◦ C)

Brine Effl. React. Effl.

Exp. Q: Na2 CO3 f

390 346 0.655 1.143 0.991 4.685 380 383
430 375 0.559 0.436 0.636 1.452 396 391
470 384 0.512 0.059 0.546 0.960 413 393
500 387 0.493 0.023 0.551 0.820 427 393

Exp. S: Na2 SO4 f

390 342 0.665 1.085 1.268 6.990 385 383
430 366 0.595 0.027 0.821 3.502 403 388
470 365 0.598 0.005 1.067 3.644 411 386
500 368 0.587 0.004 1.133 3.220 412 384
a
Temperature value taken at the end of each setpoint segment before switching to the next setpoint (compare Fig. 2).
b
Density of water at 30 MPa and at the temperature of position T13, calculated using steam tables [21].
c
Molar effluent concentration of this study converted to weight fraction.
d
Solubility of the respective salt as expected from the empirical solubility relation [20] according to the density at 30 MPa and at the temperature of T13.
e
Fluid temperature (at 30 MPa) at which the respective effluent concentration from this study would be expected; estimated using the empirical solubility relations given
by Khan and Rogak [20].
f
Feed concentration (converted to weight fraction) of Na2 CO3 and Na2 SO4 was 1.076 and 1.421 wt.%, respectively.

respond to the fluid temperatures that would have been expected
for the salt concentrations measured in the brine (TBrine Effl. ) and
the reactor effluent (TReact Effl. ), respectively. These temperatures are
higher than the measured temperature at position T13, indicating
higher temperatures at the dip tube exit and further downstream in
the salt separator, which are responsible for the remaining salt con-
centration in the reactor effluent (TReact Effl. ) and in the brine effluent
(TBrine Effl. ), respectively [11].
From these observations it can be concluded that, unlike type 1
salts described in Part 1 of this article [11], the “sticky” type 2 salts
can be separated from supercritical water but it is not possible to
recover them as a concentrated brine with the reactor design we
employed.
fluid temperature at position T13) and reached 82%. Interestingly,
the separation efficiency of this mixture, KH2 PO4 and K2 HPO4 , was
lower than the separation efficiency for an aqueous solution con-
taining only one of these salts within the same temperature range
(see Part 1 of this article [11]).
For the salts K3 PO4 and K2 HPO4 hydrolysis of the phosphate ion
was reported under supercritical conditions [11,22]. No hydrolysis
was observed for this mixture: the molar ratio of potassium to phos-
phate for both effluents, normalized to the potassium to phosphate
ratio of the feed solution, was nearly equal to one for all tempera-
ture setpoints of the salt separator (Table 6). This is not surprising
given that the mixture consisted mainly of KH2 PO4 , for which no
hydrolysis was observed [11,22].

3.2. Separation performance of two salts dissolved in water
To study the interaction of two salts, we investigated the salt
separation of mixtures of two different salts dissolved in water.
Thus the investigated systems were three components systems
(salt 1–salt 2–water). For these systems, combinations of type
1–type 1 salts and type 2–type 2 salts were studied.
3.2.1. Mixtures of two type 1 salts
3.2.1.1. The system KH2 PO4 and K2 HPO4 . The molar ratio of KH2 PO4
to K2 HPO4 of 42.5 was chosen to yield a feed solution with pH
5.5. According to the phosphate speciation, such a mixture would
consist of 0.06% H3 PO4 , 97.58% KH2 PO4 , and 2.36% K2 HPO4 . The
temperature setpoints of the salt separator were increased in steps
of 10 ◦ C to obtain a better resolution of the evolution of the salt
separation efficiency.
The conductivity of the solution and the concentrations of
potassium and phosphate at steady state (hydrogen or dihydro-
gen phosphate is detected either as phosphorus with ICP-OES or
as phosphate with anion chromatography) in the salt separator
effluent as well as the separation efficiency of these ions increase
with increasing temperature of the salt separator (Fig. 3a and b). No
salt separation was observed at the temperature setpoint of 410 ◦ C
(366 ◦ C fluid temperature at position T13). The conductivity of the
salt separator and the reactor effluents level off approximately at
the conductivity of the feed solution. At 430 ◦ C (388 ◦ C fluid tem-
perature T13) the salt mass flow rates of the salt separator effluent
and the reactor effluent were nearly equal. Hence about 50% of the
salt in the feed was recovered in the salt separator effluent. The
salt recovery (i.e. the salt separation efficiency) increased up to the
last temperature setpoint of 460 ◦ C of the salt separator (406 ◦ C
3.2.1.2. Mixtures of NaNO3 and K2 CO3 . The separation performance
of these two type 1 salts was studied for three mixtures of these
salts having different molar ratios of NaNO3 to K2 CO3 (see Table 3).
As the mixture contained two salts that exhibited a different
separation performance (compare Part 1 of this article [11]), a pref-
erential separation and recovery of one of these salts was expected.
In general, for all of these three mixtures a concentrated salt brine
could be recovered from the salt separator. This is illustrated by the
ion recoveries of the cations Na+ and K+ of these mixtures for the
salt separator effluent (separation efficiency) and for the reactor
effluent (remaining salt fraction) in Fig. 4. For the sake of clarity the
overall recoveries are not included in this figure but can be found
in Tables S4 and S5 of the supplementary materials. The overall
recovery did not close for the nitrate for all mixtures. The overall
recovery of carbonate was by far overestimated, apparently due to
the fact that nitrate reacted with the carbon support of the cata-
lyst in the reactor, forming CO2 and HCO3 − (discussed in detail in
Part 1 of this article [11]). Effective salt recovery at the salt sep-
arator, i.e. a separation efficiency greater than 50%, was observed
for 470 and 500 ◦ C setpoint temperature of the salt separator (407
and 418 ◦ C fluid temperature T13, respectively) for all of these three
mixtures. However, salt separation already began at 430 ◦ C setpoint
temperature of the salt separator for the mixtures having a molar
ratio of NaNO3 to K2 CO3 of about 1.0 and 0.5, respectively (experi-
ments V and W). But still most of the salt was collected in the reactor
effluent at this temperature setpoint, i.e. the separation efficiency
was below 50%. At 430 ◦ C salt separator setpoint temperature the
separation efficiency of potassium and sodium increased with a
decreasing ratio of NaNO3 to K2 CO3 in the feed solution. However,
that was not the case for 470 and 500 ◦ C setpoint of the salt sepa-
rator where the separation efficiency of potassium was highest for
118 M. Schubert et al. / J. of Supercritical Fluids 52 (2010) 113–124

Fig. 4. Steady state separation efficiencies for K (a) and Na (b) using a mixture of
the two type 1 salts NaNO3 and K2 CO3 of different molar ratios (experiments U–W).

efficiency of potassium the feed solution with the NaNO3 to K2 CO3

Fig. 3. (a) Electrical conductivities of the effluents of the salt separation experiment
of a mixture of KH2 PO4 and K2 HPO4 (exp. T) at different salt separator temperature
setpoints. (b) Salt separation efficiencies (recoveries in the salt separator effluent),
remaining fraction in the reactor effluent and overall recovery of K and P at steady
state for each setpoint.
the lowest ratio of NaNO3 to K2 CO3 of about 0.5, and lowest for
the intermediate NaNO3 to K2 CO3 ratio of about 1. This effect was
not observed for the separation efficiency of sodium for which the
separation efficiency for the NaNO3 to K2 CO3 ratios of about 2 and
1 (experiments U and V) was equal. But similar to the separation
ratio of 0.5 exhibited the highest separation efficiency for sodium.
A comparison of the separation efficiencies of sodium and potas-
sium suggests that there might be a preferential separation of
one of these elements (and also of one of these salts). If there
was no preferential separation of one salt, the ratio of sodium
to potassium of both effluents should be equal to the sodium to
potassium ratio of the feed solution. The molar sodium to potas-
sium ratio of both effluents of each mixture, normalized to the
molar sodium to potassium ratio of the corresponding feed solu-
tion, (cNa+ /cK+ )Effluent /(cNa+ /cK+ )Feed , is depicted in Fig. 5a. The
normalized molar nitrate to carbon ratio of the brine effluent

Table 6
Normalized effluent concentrations of the elements K and P and normalized K:P ratio of the salt separator and the reactor effluent, respectively, of experiment T at steady
state conditions for different salt separator setpoints.

TSep (◦ C) Salt separator effluent Reactor effluent

cK,Sep /cK,Feed cP,Sep /cP,Feed (K:P)Sep /(K:P)Feed cK,React /cK,Feed cP,React /cP,Feed (K:P)React /(K:P)Feed

410 0.98 0.99 0.98 0.97 0.97 1.00

420 1.68 1.66 1.02 0.87 0.87 0.99
430 3.18 3.15 1.01 0.59 0.59 1.00
440 4.83 4.80 1.01 0.24 0.24 1.00
450 5.15 5.15 1.00 0.13 0.13 1.02
460 5.40 5.42 1.00 0.14 0.14 1.02
 M. Schubert et al. / J. of Supercritical Fluids 52 (2010) 113–124 119

Fig. 5. Ratio of Na:K (a) and of NO3 − :C (b) in the brine and the reactor effluent at steady state normalized to the ratio of Na:K (or NO3 − :C, respectively) of the respective feed
solution of the salt separation experiments using a mixture of the two type 1 salts NaNO3 and K2 CO3 of different molar ratios (experiments U–W).

(cNO − /cC ) /(cNO − /cC ) is depicted in Fig. 5b. As almost no separator temperature setpoints of 470 and 500 ◦ C, and the ratio of
3 Brine 3 Feed
nitrate was found in the reactor effluent [11], the respective nor- the salt separator effluent was higher than 1.0 (except for experi-
malized nitrate to carbon ratio of the reactor effluent is not plotted. ment U at 470 ◦ C where it was nearly 1.0). The normalized molar
At 390 ◦ C setpoint temperature of the salt separator, when no sep- nitrate to carbon ratio of the brine effluent was well below 1.0 and
aration was observed, the ratio of the cations in both effluents of all decreased with higher salt separator setpoint temperatures for the
three mixtures was close to 1.0. This was also the case for the reac- experiments V and W (see Fig. 5b). For experiment U the normalized
tor effluent of all mixtures for 430 ◦ C setpoint temperature of the molar nitrate to carbon ratio decreased to values close to unity for
salt separator. Interestingly, for experiment U with a molar NaNO3 470 and 500 ◦ C salt separator setpoint temperatures but remained
to K2 CO3 ratio of 2, the normalized molar sodium to potassium ratio higher than the ratio at the temperature setpoint of 390 ◦ C.
of the salt separator effluent was about 0.7 at 430 ◦ C salt separator From this we conclude that, apparently, potassium salts can be
setpoint temperature. As the normalized sodium to potassium ratio dissolved better in supercritical water. Thus potassium is found
for this experiment was close to unity for the reactor effluent at the in a relatively higher amount in the reactor effluent. The potas-
same salt separator temperature setpoint, this would mean that sium salt enriched in the reactor effluent would have consisted
some sodium salt was held back in the salt separator, which is also mainly of KNO3 if the nitrate had not been destroyed by react-
confirmed by the evolution of the conductivity (normalized to the
conductivity of the feed solution) for experiment U in comparison
to the experiments V and W (Fig. 6). After setting the salt separator
setpoint temperature from 390 ◦ C to 430 ◦ C, the conductivity of the
salt separator effluent of experiment U increased, passed through
a maximum, and decreased to almost the value of the feed solu-
tion, while the conductivity of the reactor effluent decreased and
passed through a minimum and increased to almost the value of
the feed solution. This was not the case for experiments V and W.
An explanation might be that both salts began to separate from
the feed solution as the temperature increased. Once the fluid tem-
perature had reached a certain value, some sodium salt built up in
the salt separator and some potassium salt accumulated in the salt
separator effluent. Thus there was more potassium in the salt sep-
arator effluent compared to the feed solution. Consequently, the
conductivity of the salt separator effluent was still a bit higher than
that for the 390 ◦ C temperature setpoint of the salt separator. From
Fig. 5b it is likely that the salt which was held back at 430 ◦ C salt
separator setpoint temperature of experiment U mainly consisted
of sodium carbonate because the normalized nitrate to carbon ratio
was about 1.2 for the 430 ◦ C temperature setpoint of experiment U.
Thus the brine effluent was enriched in KNO3 at this setpoint. For
the other salt separator temperature setpoints of experiment U, the
normalized molar sodium to potassium ratio of the salt separator
effluent was close to unity (at 470 ◦ C) or slightly above (at 500 ◦ C). Fig. 6. Electrical conductivities normalized to the respective feed solution of the salt
separator and the reactor effluents of the salt separation experiments using a mix-
For all experiments U–W the normalized molar sodium to potas- ture of the two type 1 salts NaNO3 and K2 CO3 of different molar ratios (experiments
sium ratio of the reactor effluent was smaller than 1.0 for the salt U–W).
120 M. Schubert et al. / J. of Supercritical Fluids 52 (2010) 113–124

Table 7
Normalized molar ratio of the cations and the anions and pH values of each effluent of the experiments U, V, and W.

TSep Exp.: U: molar ratio NaNO3 :K2 CO3 = 2.0 Exp. V: molar ratio NaNO3 :K2 CO3 = 1.0 Exp. W: molar ratio NaNO3 :K2 CO3 = 0.5
b b
Normalized molar Effluent pH value Normalized molar Effluent pH value Normalized molar Effluent pH valueb
ratio,a ratio,a ratio,a
(cNa + cK )/(cNO3 − + cC ) (cNa + cK )/(cNO3 − + cC ) (cNa + cK )/(cNO3 − + cC )

Brine Effl. React. Effl. Brine Effl. React. Effl. Brine Effl. React. Effl. Brine Effl. React. Effl. Brine Effl. React. Effl. Brine Effl. React. Effl.

Feed 1.00 12.0 1.00 11.0 1.00 12.0

390 1.02 0.92 12.0 10.0 0.95 0.96 10.5 10.5 0.93 0.93 11.5 11.0
430 0.94 0.95 11.5 10.0 1.10 0.92 12.0 10.5 1.04 0.90 12.5 10.5
470 1.16 0.70 14.0 7.0 1.19 0.66 14.0 7.0 1.07 0.60 14.0 7.0
500 1.14 0.76 14.0 7.0 1.25 0.66 14.0 7.0 1.17 0.58 14.0 7.0
a
Normalized to the respective ratio in the feed solution.
b
All pH values measured at 0.1 MPa and 25 ◦ C using pH sticks with a graduation of 0.5 pH.

ing with the carbon support of the catalyst [11]. The salt in the
brine effluent is enriched in sodium carbonate. Although carbon-
ate was found in relatively higher amounts than nitrate in the brine
effluent, considerable hydrolysis of the carbonate salt might have
taken place, leading to an enrichment of hydroxide in the brine
and of bicarbonate or CO2 in the reactor effluent (see also dis-
cussion of the experiments J and K in Part 1 of this article [11]).
This is supported by the normalized molar cation to anion ratio,
((cNa + cK )/(cNO − + cC )) /((cNa + cK )/(cNO − + cC )) , and by
3 Effluent 3 Feed
the pH values of both effluents. If the normalized molar cation to
anion ratio is greater than 1.0 there is a lack of the anions, nitrate
and carbonate. This lack of anions might be mainly due to hydrol-
ysis of the carbonate salt. This lack would be compensated with
hydroxide ions, produced through hydrolysis of the carbonate salt,
leading to an increase in the pH value in the brine effluent (see val-
ues beyond 430 ◦ C salt separator temperature setpoint in Table 7).
The small decrease of the pH value in the brine effluent at 430 ◦ C
setpoint temperature of experiment U may be explained by some
accumulation of sodium carbonate in the salt separator at this tem-
perature setpoint (compare discussion above). The decrease of the
pH in the reactor effluent with increasing salt separator setpoint
temperature can be explained by the enrichment of bicarbonate
and CO2 in the reactor effluent produced by the reaction of the
nitrate with the carbon of the catalyst support and through hydrol-
ysis of the carbonate salt in the salt separator (compare discussion
of the experiments E–H and J–K in Part 1 of this article [11]).
Although the nitrate recovery in the salt separator effluent
increased with increasing salt separator setpoint temperature
for experiment U, for the experiments V and W no further
increase in the concentration of nitrate in the brine, i.e. the nitrate
recovery, was observed for salt separator temperature setpoints
beyond 470 ◦ C (see Table S5 in the supplementary materials). The
nitrate recovery did neither correspond to the separation effi-
ciency of sodium nor to the separation efficiency of potassium
for the three investigated mixtures of NaNO3 and K2 CO3 (refer to
Tables S4 and S5 in the supplementary materials). However, the
separation efficiency of the nitrate ion in the single salt experiments
discussed in Part 1 of this article [11] was nearly the same as that
of the corresponding cation. Thus, the discrepancy of the nitrate
separation efficiency of the single salt experiments and the NaNO3
and K2 CO3 mixtures might be an effect of the mixtures. Further
experiments are needed for the clarification of this effect.
Each salt of these NaNO3 and K2 CO3 mixtures is classified as type
1 salt [16,23]. But as these salts dissociate in aqueous solution, also
the salts KNO3 (type 1) and Na2 CO3 (type 2) might be formed in the Fig. 7. Steady state separation efficiencies in the salt separator effluent and remain-
hydrothermal environment to some extent. With this assumption, ing fractions in the reactor effluent of K (a) and Na (b) of the salt separation
supported by Fig. 5, the amount of potential type 2 salts decreased experiments using a mixture of the two type 2 salts K2 SO4 and Na2 CO3 of differ-
ent molar ratios (experiments X–Z). There was a small leak at the dip tube entrance
from experiment U to W. The mixture with the least amount of of the salt separator for the 500 ◦ C setpoint temperature of experiment Y. Thus the
type 2 salt should then exhibit the best separation efficiency. This separation efficiencies and the overall recoveries (see Tables S4 and S5) appear to
is supported by the fact that the best separation efficiencies were be lower than expected for this setting.
 M. Schubert et al. / J. of Supercritical Fluids 52 (2010) 113–124
Fig. 8. Ratio of Na:K (a) and of SO4 2− :C (b) in the brine and the reactor effluent at steady state normalized to the ratio of Na:K (or SO4 2− :C, respectively) of the respective
feed solution of the salt separation experiments using a mixture of the two type 2 salts K2 SO4 and Na2 CO3 of different molar ratios (experiments X–Z).
reached for experiment W which had the lowest ratio of NaNO3
to K2 CO3 in the feed solution (Fig. 4). However, except for 430 ◦ C
setpoint temperature of the salt separator (see Fig. 4), this did not
hold for experiments U and V.
3.2.2. Mixtures of two type 2 salts
The separation performance of a mixture of two type 2 salts
was studied using aqueous solutions of K2 SO4 and Na2 CO3 with
different molar ratios of K2 SO4 to Na2 CO3 (see Table 3).
According to the difficulty with the “sticky” type 2 salts (see
Section 3.1), the recovery of a concentrated salt brine at the salt
separator was not expected for a mixture of two type 2 salts. To
our surprise, a concentrated salt solution could be recovered with
high efficiencies for all three mixtures, which is illustrated in Fig. 7
showing the separation efficiency and the remaining salt fraction
in the reactor effluent for both of the cations, sodium and potas-
sium. The overall recoveries for these experiments are given in
Tables S4 and S5 of the supplementary materials. Interestingly,
effective salt separation for these mixtures was already observed
at a salt separator setpoint temperature of 430 ◦ C (note that for the
mixtures with NaNO3 and K2 CO3 an effective salt separation was
fist observed at higher setpoint temperatures of the salt separator).
The highest separation efficiencies (up to 95% for potassium and
up to 99% for sodium) were obtained at 500 ◦ C setpoint tempera-
ture of the salt separator for experiments X and Z. For experiment
Y, however, the separation efficiency decreased by about 7% from
the temperature setpoint of 470 ◦ C to the temperature setpoint of
500 ◦ C of the salt separator. No increase of the remaining salt frac-
tion in the reactor effluent was observed at the same salt separator
setpoint temperature. This small drop in the separation efficiency
may be attributed to a small leak at the dip tube entrance of the salt
separator at 500 ◦ C salt separator setpoint temperature.
K2 SO4 and Na2 CO3 are both classified as type 2 salts [16,23].
However, K2 CO3 (type 1, discussed in Part 1 of this article [11]) and
Na2 SO4 (type 2) might be formed to some extent in the hydrother-
mal environment. The presence of a sufficient amount of type 1 salt
might be a reason why salt separation and recovery was observed
for all three mixtures. Assuming the maximum amount of the type
1 salt K2 CO3 to be formed under hydrothermal conditions would
result in 0.05 mol/L of K2 CO3 for experiment X and 0.04 mol/L of
K2 CO3 for the experiments Y and Z. But the experiments Y and Z
121
would differ in the composition of the corresponding type 2 salts
that might be formed. For experiment Y the type 2 salts would con-
sist of 0.04 mol/L Na2 SO4 and 0.02 mol/L Na2 CO3 (same cation but
different anions), and experiment Z would have a type 2 salt com-
position of 0.04 mol/L Na2 SO4 and 0.02 mol/L K2 SO4 (same anion
but different cation). Thus, for these two experiments the systems
might consist of at least three different salt components in the near
and supercritical region, resulting in a more complex phase behav-
ior. In conclusion, the presence of a sufficient amount of type 1
salt in a salt mixture should lead to good separation and recovery
of the salts from supercritical water. Valyashko [16] gives a good
overview of several type 1–type 2 salt mixtures and the amount of
type 1 salt needed for these mixtures to show the phase behavior
of type 1 solutions supporting the above mentioned. However, the
type 2 salt mixture of K2 SO4 and Na2 CO3 investigated in our study
does not appear in that article [16].
Preferential salt separation of a brine enriched in sodium salt
was observed for the NaNO3 –K2 CO3 mixture. This effect was
also apparent, although much less pronounced, for the mixtures
of K2 SO4 and Na2 CO3 . This is illustrated by Fig. 8 showing the
molar sodium to potassium ratio of both effluents of each mix-
ture, normalized to the molar sodium to potassium ratio of the
respective feed solution, (cNa+ /cK + )Effluent /(cNa+ /cK + )Feed (Fig. 8a),
and the normalized sulfate to carbonate ratio of both effluents,
(cSO 2− /cC ) /(cSO 2− /cC ) (Fig. 8b). At the setpoint temper-
4 Effluent 4 Feed
ature of 390 ◦ C no salt separation was observed (compare Fig. 7).
Thus these normalized ratios of both effluents are nearly equal to
one for each salt mixture (Fig. 8a and b). At 430 ◦ C setpoint temper-
ature of the salt separator, when an effective salt separation was
observed, a higher amount of sodium salt was recovered at the salt
separator (the normalized sodium to potassium ratio is greater than
1). Correspondingly, the concentration of potassium salt was higher
in the reactor effluent. This effect disappeared for experiment X
(the concentrations of K2 SO4 and Na2 CO3 in the feed solution were
the same) at higher salt separator temperatures where the normal-
ized sodium to potassium ratio equaled one in the reactor effluent
and was close to one in the brine effluent as well. As illustrated
in Fig. 8b, the brine effluent was enriched in a sulfate salt (most
likely sodium sulfate, compare Fig. 8a) for all experiments carried
out with the K2 SO4 and Na2 CO3 mixtures. The reactor effluent,
however, showed an excess in a (bi-)carbonate salt (most likely
122 M. Schubert et al. / J. of Supercritical Fluids 52 (2010) 113–124

Table 8
Normalized molar ratio of the cations and the anions and pH values of each effluent of the experiments X, Y, and Z.

TSep Exp.: X: molar ratio K2 SO4 :Na2 CO3 = 1.0 Exp. Y: molar ratio K2 SO4 :Na2 CO3 = 0.7 Exp. Z: molar ratio K2 SO4 :Na2 CO3 = 1.6
b b
Normalized molar Effluent pH value Normalized molar Effluent pH value Normalized molar Effluent pH valueb
ratio,a ratio,a ratio,a
(cK + cNa )/(cSO 2− + cC ) (cK + cNa )/(cSO 2− + cC ) (cK + cNa )/(cSO 2− + cC )
4 4 4

Brine Effl. React. Effl. Brine Effl. React. Effl. Brine Effl. React. Effl. Brine Effl. React. Effl. Brine Effl. React. Effl. Brine Effl. React. Effl.

Feed 1.00 11.5 1.00 11.5 1.00 11.5

390 0.95 1.02 11.5 11.5 0.99 1.07 11.5 11.5 0.96 0.97 10.5 11.5
430 1.07 0.81 14.0 10.5 1.11 0.89 12.5 10.0 1.08 0.79 12.5 10.0
470 1.08 0.55 14.0 7.0 1.23 0.60 14.0 7.0 1.09 0.53 14.0 7.0
500 1.08 0.50 14.0 7.0 1.11 0.55 14.0 7.0 1.08 0.47 14.0 7.0
a
Normalized to the respective ratio in the feed solution.
b
All pH values measured at 0.1 MPa and 25 ◦ C using pH sticks with a graduation of 0.5 pH.

potassium (bi-)carbonate). This large excess in inorganic carbon ones investigated in the experiments X–Z can be made with the
in the reactor effluent might again result from the hydrolysis of help of Fig. 9. We plotted the sulfate concentration (converted to
a carbonate salt in the salt separator at supercritical conditions mg/L) in the reactor effluent of experiment X against the fluid tem-
(see discussion above and [11]), leading to an increase in the pH perature at position T13. Note that this graph is not the solubility of
value in the brine effluent and to a respective decrease of the pH sulfate at the plotted temperature. This relationship is depending
value in the reactor effluent for increasing salt separator setpoint on the specific design of our salt separator and on the operating
temperatures, summarized in Table 8. This is also supported by conditions. As such, it is a useful illustration for the target to be
the development of the normalized molar cation to anion ratio, reached by the salt separator. For the salt separator temperature
((cK + cNa )/(cSO 2− + cC )) /((cK + cNa )/(cSO 2− + cC )) of the setpoints of 430–500 ◦ C an exponential decay in the sulfate con-
4 Effluent 4 Feed
effluents. The increase of this ratio in the brine effluent with centration versus the temperature was assumed and fitted to the
increasing salt separator temperature displays the loss of carbon- data points. The point at 390 ◦ C salt separator setpoint temperature
ate in the brine effluent due to hydrolysis, leading to an enrichment was not considered in this fit, as no salt separation was observed
of sulfate and hydroxide (which is not included in this ratio) in the at this temperature, indicating that the sulfate concentration in the
brine effluent, and to an enrichment of bicarbonate in the reactor feed was below its solubility limit at this temperature setpoint. The
effluent. extrapolation of this fit reveals that a fluid temperature at position
From these observations we conclude that a slightly preferen- T13 of at least 468 ◦ C is required to obtain less than 1 mg/L sulfate in
tial separation and enrichment in the brine effluent of a sodium the reactor effluent. This fluid temperature is in principle available
salt (most likely sodium sulfate, compare Fig. 8) remained for the inside the salt separator at setpoint temperatures higher than ca.
experiments Y and Z, especially at 500 ◦ C salt separator setpoint 480 ◦ C (see Fig. 2 of Part 1 of this article [11]). However, the flow
temperature. This again suggests a higher solubility of potassium characteristics in the salt separator are such that salt precipitation
salts in supercritical water. does not occur at the highest fluid temperature. Peterson [26] has
It is possible that the formation of double salts inside the recently analyzed the hydrodynamic situation inside the reverse-
salt separator, such as m Na2 SO4 ·nK2 SO4 (“NaKSO4 ”) [24] or
K2 CO3 ·Na2 CO3 (“NaKCO3 ”) [25], might have contributed to the
observed separation performance of the K2 SO4 and Na2 CO3 mix-
tures as well. Correspondingly, double salts might have formed
also in the system NaNO3 and K2 CO3 (experiments U–W). However,
we did not attempt to determine whether such double salts were
formed or to what extent they might have influenced the separation
performance of the K2 SO4 and Na2 CO3 mixtures.
In contrast to the NaNO3 –K2 CO3 mixtures discussed above, the
anion recoveries in the salt separator and the reactor effluent for
the K2 SO4 –Na2 CO3 mixtures show the same trends as the corre-
sponding cations (see Table S5 of the supplementary materials).
However, carbonate was lost to some extent, shown by its non-
closing overall recovery, due to hydrolysis discussed above and in
Part 1 of this article [11].
As sulfate or sulfur species originating from sulfate salts were
found to poison the catalyst in the hydrothermal gasification of wet
biomass [5], an important result of this study is that it is possible
to continuously precipitate and recover sulfate from a salt mixture
with high efficiencies. To obtain reasonable catalyst lifetimes only
a very small amount of sulfate (less than 1 ppm) can be tolerated
in the reactor feed. In this study, values of 0.5–0.6 mmol/L sulfate
(corresponding to 48–58 mg/L SO4 2− or 16–19 mg/L S, respectively) Fig. 9. Sulfate concentrations in the reactor effluent of experiment X at different
were still found in the reactor effluent at 500 ◦ C salt separator set- salt separator temperature setpoints/fluid temperatures at position T13. The black
line corresponds to an exponential fit for 430–500 ◦ C salt separator setpoint tem-
point temperature (417 ± 1 ◦ C fluid temperature at position T13).
peratures. This fit was extrapolated to higher temperatures to tentatively estimate
An estimate of the minimum fluid temperature required for reduc- the minimum temperature required for achieving less than 1 ppm of sulfate in the
ing the sulfate concentration to 1 ppm from mixtures similar to the reactor effluent (at a pressure of 30 ± 0.5 MPa).
 M. Schubert et al. / J. of Supercritical Fluids 52 (2010) 113–124
flow vessel. This knowledge will be used to improve the design of
the salt separator to bring the maximum outlet temperature closer
to the maximum fluid temperature inside the salt separator. This
would enable higher separation efficiencies to be reached without
excessive heating effort. Note that in complex biomass feeds the
presence of other salts and organic matter will also influence the
separation performance of the salts.
3.3. Some remarks on salt solubility and solubility modeling
Several studies have focused on the experimental determina-
tion of the solubility of a single salt in water (binary system) at
near-critical and supercritical conditions and correlate these solu-
bility data to empirical [20] or semi-empirical [22,27,28] models.
Common empirical and semi-empirical approaches have been crit-
ically reviewed by Leusbrock et al. [29]. Although (semi-) empirical
relations describe the solubility behavior of a salt accurately within
the range of available experimental data, extrapolation beyond the
experimental data may lead to large errors in the prediction of the
salt solubility. Also, it is impossible to predict the solubilities of
the salts in any mixture at hydrothermal conditions with such an
approach [29].
The thermodynamic properties of a salt–water system can be
described with the help of equations of state (EOS). For the sys-
tems NaCl–H2 O, KCl–H2 O and NaCl–KCl–H2 O equations of states
for hydrothermal conditions were presented by Anderko and
Pitzer [30,31]. While the prediction of the thermodynamic prop-
erties of the binary systems agreed well with experimental data,
vapor phase compositions of ternary NaCl–KCl–H2 O systems could
be described only qualitatively due to a lack of experimental
data [31]. As an advantage, the EOS can be extended to mul-
ticomponent mixtures including organic compounds. However,
such extensions increase the complexity of the EOS considerably
[29].
In this study we have investigated the precipitation and sep-
aration of solutions containing either two type 1 salts (refer to
Section 3.2.1) or two type 2 salts (refer to Section 3.2.2). We con-
cluded that the observations for the mixtures of NaNO3 –K2 CO3
(both type 1) and K2 SO4 –Na2 CO3 (both type 2) could be explained
by a formation of mixtures of type 1 and type 2 salts from the
initial ones at supercritical conditions. According to Valyashko
[16,32] the addition of a sufficient amount of a type 1 salt to
a solution of a type 2 salt would change the solubility behavior
of the type 2 salt under hydrothermal conditions, leading to an
increased solubility of the type 2 salt with increasing tempera-
ture in the brine of the type 1 salt. An example of such a behavior
was given for the system NaCl–Na2 SO4 –H2 O by DiPippo et al.
[33].
The phase behavior of ternary systems is very complex due to
the occurrence of numerous phase equilibria in the range of near-
critical and supercritical water [9,16,33]. The phase behavior of a
ternary system (salt 1–salt 2–water) may be estimated if the com-
plete phase diagrams of the respective binary systems are known
[16]. However, the prediction of the separation performance of
salt mixtures as discussed herein or of salt solutions with a com-
position similar to a real biomass feedstock requires a different
approach, as these systems are likely of higher than the ternary
dimension.
Although we found no phase data on the specific ternary
systems we studied, we assume that the type 2 salts in our
mixtures dissolved in the brine of the type 1 salts that formed
under hydrothermal conditions in our experiments. Apparently,
this liquid-like brine solution exhibited a behavior similar to
the single type 1 salts discussed in Part 1 of this article
[11] and thus could be recovered from the system with high
efficiencies.
123
4. Summary and conclusions
We investigated the continuous salt separation and recovery
from supercritical water for different binary type 2 salt solutions
and solutions consisting of mixtures of either two type 1 salts or
two type 2 salts.
In contrast to type 1 salts, single type 2 salts could not be recov-
ered as a concentrated brine, although they were separated from
supercritical water. Type 2 salts form solids under these condi-
tions. When precipitating, they stick to the hottest part – the salt
separator wall – and lead to plugging of the salt separator.
Mixtures of two type 1 salts behaved similarly to solutions con-
taining only one type 1 salt. But, surprisingly, for the mixture of
NaNO3 and K2 CO3 we found a preferential separation and recovery
of sodium carbonate.
To our surprise – in contrast to single type 2 salt solutions –
salt separation and recovery of a concentrated brine was possible
for an aqueous solution containing the two type 2 salts K2 SO4 and
Na2 CO3 of different molar ratios. However, in that special case salt
nucleation from these solutions at supercritical conditions might
lead to partial formation of a certain amount of type 1 salt, leading
to the unexpected separation performance.
From these experiments we conclude that it is not possible to
predict the separation performance of a given salt mixture just by
knowing the separation performance of the corresponding single
salt solutions. At present it is still necessary to perform salt separa-
tion experiments with salt solutions of a composition similar to a
real biomass feedstock before performing gasification experiments
with that feedstock. Clearly, the salt separation is strongly affected
by the phase behavior of the salt solutions. Future work should
address the investigation of the phase behavior of systems con-
taining salts relevant to the hydrothermal gasification of biomass.
In addition, in situ spectroscopic techniques would help to under-
stand the nucleation behavior of salts from supercritical water on a
molecular level. However, it is not clear yet if the separation perfor-
mance of a solution of a specific salt or salt mixture can be explained
solely by its phase behavior.
Acknowledgements
We thank Axpo Naturstrom-Fonds for financial support. Fur-
ther the authors gratefully acknowledge E. De Boni, T.-B. Truong,
A. Schuler, and A. Frei for experimental support and M. Branden-
berger, J. Müller, C. Ludwig, S. Stucki, and A. Wokaun for valuable
discussions.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.supflu.2009.10.003.
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