You are on page 1of 21

University of Groningen

Removal of inorganic compounds via supercritical water


Leusbrock, Ingo

IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from
it. Please check the document version below.

Document Version
Publisher's PDF, also known as Version of record

Publication date:
2011

Link to publication in University of Groningen/UMCG research database

Citation for published version (APA):


Leusbrock, I. (2011). Removal of inorganic compounds via supercritical water: fundamentals and
applications [Groningen]: Rijksuniversiteit Groningen

Copyright
Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the
author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).

Take-down policy
If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately
and investigate your claim.

Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the
number of authors shown on this cover page is limited to 10 maximum.

Download date: 25-08-2018


Chapter 6

The solubilities of phosphate and


sulfate salts in supercritical water

This chapter has been published as:


Leusbrock, I., Metz, S. J., Rexwinkel, G., and Versteeg, G. F.; The solubilities of phos-
phate and sulfate salts in supercritical water ; The Journal of Supercritical Fluids 54(1),
1-8.

- 129 -
Chapter 6 ∥ Phosphate and sulfate salts

Abstract

Inorganic compounds are regularly present in aqueous streams. To understand


their influence and behavior on these streams at supercritical conditions, little to
no property data is available, which can be used as starting point for further
research or application design. Since inorganic compounds tend to precipitate
at these conditions, scaling, blocking and erosion can occur as a consequence.
Furthermore, a separation of (precious) compounds from the bulk stream due
to the precipitation is possible. Here, phosphate compounds are regarded as
interesting for further investigation since resources are assumed to be depleted
in future. As phosphate is present in many waste streams, these could be used
as sources for recoverable phosphate. Resulting from these facts and options,
a proper understanding and knowledge of these systems is important for later
industrial applications. Therefore, the authors have investigated the behavior of
salts (e.g. NaCl, NaNO3 and MgCl2 ) in supercritical water in previous works.
To extend this knowledge, the solubilities of the sulfate salts MgSO4 and
CaSO4 in a range of 18.8 - 23.2 M P a and 655 - 675 K as well as of the phosphate
salts Na2 HPO4 , NaH2 PO4 and CaHPO4 in a range of 20.5 - 24.2 M P a and
665 - 690 K were investigated in this work with a continuous flow method in
continuation of former work of the authors. The solubilities were compared with
existing data available from open literature. A quantitative correlation on base of
a phase equilibrium between the present phases was used to describe the behavior
and to compare it with previous results. For the investigated calcium salts, CaSO4
and CaHPO4 , it was found that a significant solubility decrease already happens
at subcritical conditions resulting in precipitation in unwanted locations. For the
remaining compounds, a parallel hydrolysis reaction was found as could be seen
from a change in pH in the effluent stream.

Keywords: Phosphates, Solubility, Sulfates, Supercritical water

- 130 -
6.1 ∥ Introduction

6.1 Introduction
Supercritical water (SCW) is regarded as one of the most promising and interesting
solvents / environments for future industrial applications such as hydrothermal conver-
sion of biomass (1; 2), destruction of waste sludge and organic waste compounds (3; 4),
particle formation on a micro- and nanoscale (5; 6), reaction media for polymerizations
and conversion processes (7; 8) and separation of inorganic compounds. Due to funda-
mental changes in properties at supercritical conditions (critical temperature Tc = 647
K, critical pressure pc = 22.1 M P a), SCW varies to a large degree in its properties
compared to the common phases liquid and vapor. The additional benefit of supercriti-
cal fluids and SCW is the fact that properties like diffusion rate, density and viscosity are
adjustable in the supercritical regime (9; 10). As a result of the comparably harsh criti-
cal conditions of water1 and a limited number of industrial and commercial installations,
available property data on systems containing supercritical water is scarce in comparison
to other supercritical fluids.
Inorganic compounds can be found in a majority of aqueous streams. At supercrit-
ical conditions, these compounds tend to precipitate or to form vapor or liquid phases
saturated in salt. This precipitation can lead to scaling and plugging in installations and
therefore has to be controlled or avoided (11; 12). First investigated in connection with
supercritical water oxidation (SCWO) (13; 14), it became obvious in later applications
like supercritical water gasification (SCWG) that the presence of inorganic compounds
can have a major influence on the reaction and the process itself (e.g. as a catalyst
(15)). Furthermore, severe problems can occur for a continuous long-term process (e.g.
corrosion (16; 17), increased pressure drops due to scaling (12), catalyst poisoning (18)).
Therefore, concepts were developed to avoid the formation of such a solid phase (e.g.
different reactor modifications (19; 20)) or to separate inorganic compounds in an inte-
grated treatment step before the actual process step (18; 21). For the design of these
new concepts and even more sophisticated ones like a fractionation of different salt
fractions, it is vital to have a sound understanding of the solubility of these inorganic
compounds and their influence and behavior. One of the group of compounds, which are
of interest for a separation from other compounds, are phosphates. Phosphates are part
of many waste streams, which represents a potential source for recoverable phosphate
(22). As phosphate resources are limited and a shortage or even a depletion of global

1
Carbon dioxide as the most frequently applied supercritical fluid has a critical temperature Tc =
304 K and a critical pressure pc = 7.4 M P a.

- 131 -
Chapter 6 ∥ Phosphate and sulfate salts

resources is expected, new ways have to be found to recover phosphate and to guarantee
sufficient fertilizers for global food production.
In previous works of the authors, monovalent salts (alkali nitrates and chlorides (23;
24)) and bivalent salts (calcium and magnesium chloride (25)) were investigated. Here,
a continuous flow method was used to investigate the solubilities of these compounds.
In these studies, different quantitative approaches to describe solubilities in SCW were
compared. The behavior and a quantitative description for the solubility of monovalent
chloride and nitrate salts and double-valent chloride salts was presented. In the course
of this study, the solubilities and behavior of the bivalent salts MgSO4 and CaSO4 in a
range of 18.8 - 23.2 M P a and 655 - 675 K as well as of the mono- / bivalent cation
/ triple-valent anion phosphate salts Na2 HPO4 , NaH2 PO4 and CaHPO4 in a range of
20.5 - 24.2 M P a and 665 - 690 K was object of the investigations. The experimental
data was correlated with an approach derived in an earlier work (23). The results of
this correlation are compared with previous results of the authors as well as with data of
similar compounds available in literature (26).

6.2 Theoretical background

6.2.1 Correlation of the experimental data


For quantitative description of the solubilities, an approach on base of a phase equilibrium
between the present phases is applied (23; 27). In this approach, the solid phase and the
supercritical fluid are assumed to form an equilibrium depending on the conditions in the
system (23). Thereby, a description of the equilibrium between the phases is possible in
the following manner:

a ⋅ M ec ∗ m ⋅ H2 O(f ) + b ⋅ X d ∗ p ⋅ H2 O(f ) ⇌ M ea Xb ∗ n ⋅ H2 O(f )


M ea Xb ∗ n ⋅ H2 O(f ) ⇌ M ea Xb (s) + n ⋅ H2 O(f )
αM ea Xb ∗ n⋅H2 O(f )
Ô⇒ Ks = (6.1)
αM ea Xb (s) ⋅ αHn O(f )
2

Me and X resemble the salt cation / the salt anion; a and b is the number of ions in
the salt molecule; c and d their valency; s and f refer to the solid and fluid phase; n, m
and p to the number of water molecules. For this approach it is furthermore assumed
that a formation of the solid phase occurs via the associated complex and not directly

- 132 -
6.3 ∥ Experimental

via dissociated ions (28). For the equilibrium constant Ks , several simplifications can be
made. Interaction between the species in the system is neglected; the activity coefficient
of the solid phase is assumed as unity. The fluid phase is treated as an ideal one. A
more extensive description of this approach can be found be elsewhere (23; 24; 27). As a
result of these assumptions, the solubility of inorganic compounds in supercritical water
can be described in the following way:

mM ea Xb ∗ n⋅H2 O(f )
Ks∗ ≈
1 ⋅ ρnm, H
2 O(f )

Ô⇒ mM ea Xb ∗ n⋅H2 O(f ) = Ks∗ ⋅ ρnm, H (6.2)


2 O(f )

Substituting the equilibrium constant under usage of a van‘t Hoff-like expression leads
to the following expression:

mM ea Xb ∗ n⋅H2 O(f )
Ks∗ ≈
1 ⋅ ρnm, H
2 O(f )

Ô⇒ mM ea Xb ∗ n⋅H2 O(f ) = Ks∗ ⋅ ρnm, H


2 O(f )

Ô⇒ log mM ea Xb ∗ n⋅H2 O = log Ks∗ + n ⋅ log ρm, H2 O


∆solv H ∆solv S
= − + + n ⋅ log ρm, H2 O (6.3)
R⋅T R
For a more convenient interpretation of the parameters, a description on an amount of
substance base is chosen. Ks and Ks∗ are the equilibrium constant and the equilibrium
constant including the simplifications. R is the universal gas constant, T the system
temperature, m the molality, ρ the density, n the coordination number. The Gibbs
energy of solvation, ∆solv G, the enthalpy of solvation, ∆solv H, and the entropy of
solvation, ∆solv S are assumed as independent of the system parameters temperature,
pressure and density. The density of pure water is calculated via the IAPWS95 equation
of state (29). Experimental data was fitted to the parameters ∆solv H, ∆solv S and n to
quantitatively describe the solubility. A more detailed description on this approach can
be found elsewhere (23; 24).

6.3 Experimental
For the measurements of the solubilities of the phosphate and sulfate salts, a continuous
flow method was applied like in the previous works of the authors. The most important

- 133 -
Chapter 6 ∥ Phosphate and sulfate salts

details of the method and setup are presented in the following; a more detailed description
can be found elsewhere (23; 24).
The setup is designed for an operation up to 25 M P a and 723 K. A scheme of the
setup can be found in Figure 6.1. Heat was provided by a custom-made oven and a
pre-heater; for pressurization and flow, a HPLC Pump was used (LabAlliance Series III,
LabAlliance, USA). An U-tube was installed inside the oven with a length of 265 mm,
an inner diameter of 4.6 mm and an outer diameter of 6.35 mm. The temperature
inside the oven was measured at inlet, middle and outlet position by standard Type K
thermocouples (relative uncertainty 0.25 %). The pressure inside the setup is measured
with a pressure sensor (Keller PA23H, relative uncertainty 0.2 %). The material of choice
for all heated parts was Hastelloy, the diameter of every tubing was 1/16” (=1.588 mm)
if not mentioned otherwise.

Analysis
TI-6 temperature
Back Pressure
Pressure Regulator Relief Valve

HPLC pump PI-1


Preheater
Cooling
Temperature control Analysis
oven TI-5 CI-1 and
Conduc- sampling
Outlet
TI-1 TC-1 tivity
Supply vessel temperature
measurement
Preheater
temperature

Filter
2 m

TI-2 Oven Outlet


TI-4 temperature
Oven Inlet
temperature

Salt
column
Oven Center
Oven TI-3 temperature

Figure 6.1 ∥ Scheme of the experimental setup

The feed stream enters the U-tube, where an oversaturation of the feed stream de-
pending on the system conditions (pressure, temperature, density) and the feed con-
centration can occur. If so, the exceeding amount starts to precipitate and form an
additional phase till an equilibrium in the system has established. The stream exits the
U-tube at an equilibrium state with a composition resulting from the system conditions.
After cooling and depressurization, samples can be taken. The analysis of these samples
is done via an inductive coupled plasma atom emission spectrometer (ICP, Perkin-Elmer
Optima 5300DV, Perkin-Elmer, USA, uncertainty < 2 % for all investigated species) for

- 134 -
6.4 ∥ Results and Discussion

the concentrations of Na, Ca, Mg and P. Ionic chromatography (IC, Metrohm 741 Com-
pact IC, Metrohm AG, Switzerland, uncertainty < 5 % for all investigated species) was
used for measurement of the SO4 and PO4 concentration. Conductivity measurement of
the outlet stream was used for the verification of an equilibrium state in the column. pH
measurements of the samples were performed using an standard pH electrode (WTW
pH/Cond 340i/SET, WTW Wissenschaftlich-Technische Werkstätten GmbH, Germany,
uncertainty after calibration ± 0.01). The outlet temperature (TI-4 in Fig. 6.1) and
the pressure at the pressure sensor (PI-1 in Fig. 6.1) were used for the calculation of
the density in the system. The feed solution was prepared with deionized water and
analytical grade compounds (Boom B.V., The Netherlands).

6.4 Results and Discussion

6.4.1 Experimental results phosphate salts


The solubility of Na2 HPO4 , NaH2 PO4 and CaHPO4 was investigated in a range of 20.5
- 24.2 M P a and 665 - 690 K. For the sodium phosphates a feed concentration of 0.05 M
was used; for CaHPO4 a feed concentration of 0.05 - 0.5 mM was used2 . Na2 HPO4 and
NaH2 PO4 showed occasional plugging, apparently independent of temperature, pressure
and length of the experiment. The plugging in this case occurred at the filter in the outlet
section, which could be removed by rinsing with nitric acid (cf. Fig. 6.1). CaHPO4 on
the other hand showed severe plugging in the preheater and the inlet section. Although
the preheater was switched off to avoid plugging in later experiments with CaHPO4 ,
plugging of the preheater and the inlet section occurred before an equilibrium in the
column was achieved. Therefore, no further experiments on CaHPO4 were performed.
Since CaHPO4 has a low solubility at ambient state (∼200 mg ⋅ L−1 (30)), a further
decrease to minimal solubilities at elevated temperatures was to be expected resulting in
the observed plugging. For all experiments with phosphate salts, the composition of the
samples was analyzed in regard of the content of Na+ , P and PO3−
4 . Each data point
results from the experimental results of four to six individual samples at one temperature
and pressure.
Phosphates form a complex conjugated acid / base system of the acid / base pairs of
H3 PO4 , H2 PO−4 , HPO2− 3−
4 and PO4 (cf. Fig. 6.2), wherein all forms act as weak acids
/ bases and as buffer (also see Eq. 6.4 to 6.6).
2
The feed concentration was decreased in order to avoid plugging

- 135 -
Chapter 6 ∥ Phosphate and sulfate salts

Figure 6.2 ∥ Relative fraction of phosphate species as a function of pH

Figure 6.3 ∥ Solubility of Na2 HPO4 as a function of density; ○, this work; dashed line
represents the description of the experimental data with Eq. 6.3

H3 P O4 + H2 O ⇋ H2 P O4− + H3 O+ (pK = 2.12) (6.4)


H2 P O4− + H2 O ⇋ HP O42− + H3 O+ (pK = 7.21) (6.5)
HP O42− + H2 O ⇋ P O43− + H3 O+ (pK = 12.63) (6.6)

- 136 -
6.4 ∥ Results and Discussion

By changes of the pH in the system, the equilibria and the relative fractions of the
different steps can be changed.

(a)

(b)

Figure 6.4 ∥ Solubility of sodium and phosphate (a) and phosphorus and phosphate
(b) as function of density for the experiments on Na2 HPO4 ; ○ corresponds to sodium
concentration; ◻ corresponds to phosphorus concentration; ▽ corresponds to phosphate
concentration

Disodium hydrogen phosphate

Figure 6.4 shows the concentrations of the three analyzed compounds (Na+ , P and PO3−
4 )
as a function of the molar density. Each data point consists of five samples of one ex-

- 137 -
Chapter 6 ∥ Phosphate and sulfate salts

perimental run at one set temperature and pressure. The pH value for these samples
were in the range of 6.5 - 7.5, while the pH of the 0.05 M feed solution was calculated
as 9.18 (calculated with OLIT M , a simulation software for electrolyte chemistry). As can
be seen, the concentration of phosphorus (analyzed by ICP) and phosphate (analyzed by
IC) coincide within experimental errors. It can be concluded that no decomposition of
the phosphate happened. According to the molar composition of Na2 HPO4 , a factor 2
between the concentration of phosphate / phosphorus to sodium was to be expected in
the samples. Regarding the sodium concentration, one can see that all measured con-
centrations (with one exception) were only slightly above the corresponding phosphorus
/ phosphate concentration and did not reach a ratio of 2.
A possible explanation for this could be a parallel hydrolysis like described in the
following equation:

N a2 HP O4 + H2 O ⇋ N aOH ↓ +N aH2 P O4 (6.7)

The hereby produced sodium hydroxide is assumed to have a lower solubility than
the other present compounds and to precipitate at the experimental conditions. The
effluent stream consequently would leave the system at a lower sodium / phosphate
ratio than the influent stream. A continued reaction to phosphoric acid can be excluded
since the effluent pH was between 6.5 and 7.5. Resulting from this, only H2 PO4−
and HPO42− are present in the system (cf. Fig. 6.2). A correction of the cation
concentration like proposed in Eq. 6.9 does not lead a significant increase in the cation
concentration. It is assumed that the buffer capacity of the system prevents a further
decrease in pH. Thereby, a direct correlation of the pH to the amount of precipitated
NaOH cannot be derived. For the further quantitative description of the solubility, the
sodium concentration is used in accordance to previous works. One has to be aware that
the actual solubility of Na2 HPO4 is underestimated to a certain degree by this approach.
The sodium concentration for the experiments with Na2 HPO4 can be found in Figure
6.3. Furthermore included in this graph is the description of the experimental data with
Eq. 6.3. As can be seen, the approach is in good agreement with the experimental data.
More details on the approach and fitting procedure can be found in section 6.2 and in
previous works (23; 24).
The actual experimental data containing temperature, pressure, pH and sodium con-
centration can be found in Table D.1; the parameters for Eq. 6.3 for Na2 HPO4 can be
found in Table 6.1.

- 138 -
6.4 ∥ Results and Discussion

Sodium dihydrogen phosphate

Figure 6.5 shows the concentrations of Na+ and PO3−


4 as a function of the molar density.
Each data point consists of five samples of one experimental run at one set temperature
and pressure. The data for the phosphorus concentration coincides to a high degree
with the phosphate concentration and is therefore not included in this figure. The pH
value for these samples were in the range of 2.7 - 3.2, while the pH of the 0.05 M
feed solution was calculated as 4.54 (calculated with OLIT M , a simulation software for
electrolyte chemistry). According to the molar composition of NaH2 PO4 , the concentra-
tions of phosphorus / phosphate and sodium were expected to be equal. Yet, all sodium
concentrations were below the corresponding phosphorus / phosphate concentrations.
A hydrolysis reaction is assumed as the reason for this in accordance with previous ob-
servations (25). This hydrolysis leads to a formation of NaOH, which precipitates. The
parallel formed HCl stays in solution and leaves the system with the effluent. This leads
to a decrease in pH as can be found for these experiments. A correction of this hydrolysis
reaction is possible with the following approach:

mH3 O+ = mH2 P O4− = mN aOH


mtotal (N a) = manalyzed (N a) + mHydrolysis (N a)
= manalyzed (N a) + m(N aOH)
= manalyzed (N a) + 10−pH (6.8)

As can be seen from Figure 6.5, the correction shows in this case a good coincidence
with the results for the phosphate / phosphorus results. For further evaluation of the
results, the corrected sodium concentration is used. The corrected sodium concentration
for the experiments with NaH2 PO4 can be found in Figure 6.6. Furthermore included in
this graph is the description of the experimental data with Eq. 6.3. As can be seen, the
approach is in good agreement with the experimental data. More details on the approach
and fitting procedure can be found in section 6.2 and in previous works (23; 24).
The actual experimental data containing temperature, pressure, pH and corrected
sodium concentration can be found in Table D.2; the parameters for Eq. 6.3 for
Na2 HPO4 can be found in Table 6.1.

- 139 -
Chapter 6 ∥ Phosphate and sulfate salts

(a)

(b)

Figure 6.5 ∥ Solubility of sodium and phosphate (a) and comparison between the cor-
rected solubility of sodium and the solubility of phosphate (b) as function of density for
the experiments on NaH2 PO4 ; ○ corresponds to sodium concentration; ▽ corresponds
to phosphate concentration; △ corresponds to corrected sodium concentration

Comparison phosphate salts

Figure 6.7 shows a comparison of the results for the phosphate salts Na2 HPO4 and
NaH2 PO4 presented in this work and the results for KH2 PO4 by Wofford et al. (26).
The comparison shows that the solubility of potassium phosphate in supercritical water
is lower than the solubility for sodium phosphates. This agrees with the assumption that
the molecule size or in this case the cation size is related to the solubility as presented

- 140 -
6.4 ∥ Results and Discussion

Figure 6.6 ∥ Solubility of NaH2 PO4 as a function of density; ○, this work; dashed line
represents the description of the experimental data with Eq. 6.3

Figure 6.7 ∥ Comparison of the solubilities of Na2 HPO4 , NaH2 PO4 (this work) and
KH2 PO4 (26) as function of density; dashed line corresponds to Na2 HPO4 ; solid line
corresponds to NaH2 PO4 ; dashed-dotted line corresponds to KH2 PO4

in previous works (24; 31). In these works, a direct relation between the cation of the
investigated chloride salts and the actual solubility was found (Li > Na > K). As ions

- 141 -
Chapter 6 ∥ Phosphate and sulfate salts

are present in supercritical water only to a small amount, the majority of the non-water
species present is associated as molecules and complexes. To keep these molecules in
solution, hydration has to occur. This hydration is due to the decreased amount and
strength of hydrogen bondings in supercritical water less present than at ambient state.
Therefore, a hydration of larger molecules is more difficult as more hydrogen bondings
have to be established over a larger distance (24).
Upon a comparison between the solubilities of KH2 PO4 and the two sodium phos-
phates, it can be seen that the solubility of KH2 PO4 is lower in agreement with the
findings for the alkali chlorides and nitrates. As one compares the solubilities of the
phosphates investigated in this work, NaH2 PO4 has a slightly higher solubility than
Na2 HPO4 in the investigated density range. It can be concluded here as well that the
molecule size is of influence since Na2 HPO4 and the resulting hydration sphere is larger
by a small amount than NaH2 PO4 and thereby resulting in the lower solubility.

6.4.2 Experimental results sulfate salts

Two sulfate salts that are commonly found in water streams, MgSO4 and CaSO4 , were
investigated in the range of 18.8 - 23.2 M P a and 655 - 675 K. CaSO4 has a low
solubility product at ambient conditions (Ksp = 4.93 ⋅ 10−5 (30)), while the solubility
of MgSO4 is comparably high (Ksp = 4.67 (30)). Therefore, a low feed concentration
(1 mM and below) was used to avoid plugging. Despite this low feed concentration,
plugging occurred in and just before the preheater for both salts. The tubing in the
preheater has a diameter of 1.588 mm and thereby only a small cross section. A further
reduction in concentration did not solve this issue and just postponed the point of
plugging by several minutes to hours. To solve this problem, the preheater was turned
off in order to avoid precipitation before the solution enters the oven. This was successful
for MgSO4 , yet not for CaSO4 . Due to thermal conductance, parts of the preheater
and parts just after the preheater were heated up apparently far enough to precipitate
parts of the feed solution in case of CaSO4 . This indicates a higher solubility of MgSO4
at supercritical pressures and slightly elevated temperatures in comparison to CaSO4
similar to the behavior of CaHPO4 (cf. previous section). Therefore, only results for
the measurements of MgSO4 can be presented here. Attempts to remove the plugging
via ultrasound and rinsing with concentrated nitric acid / Piranha solution (3:1 conc.
H2 SO4 to 30 % H2 O2 ) did not succeed for both salts.

- 142 -
6.4 ∥ Results and Discussion

Magnesium sulfate

The experimental data for the measurements of MgSO4 can be found in Figure 6.8.
The overall solubilities are low and in the range of 10−4 to 10−5 mol ⋅ kg −1 . Thereby, the
concentrations were in the lower detection range of the analytical methods applied here.
Furthermore included in this graph is the quantitative description of the experimental
data via Eq. 6.3.
As can be seen, the approach is in good agreement with the experimental data. For
all samples, a pH value of between 3.9 and 4.6 was measured, while the feed solution of
1 mM MgSO4 a pH value of 6.98 was determined (calculated with OLIT M , a simulation
software for electrolyte chemistry). This decrease in pH indicates the occurrence of a
parallel hydrolysis reaction (25). Nevertheless, a correction of the cation concentration
for a parallel hydrolysis reaction as done for MgCl2 and CaCl2 was not performed due
to the following. The values for the cation and anion concentration coincide and the
deviation between the anion and cation concentration was within the experimental error
(cf. Fig. 6.9). Therefore, no excess amount of one of the species magnesium or sulfate
was present in the sample which would make a correction necessary. If one performs
a correction of the cation concentration for the hydrolysis as proposed in Leusbrock et
al. (25) (also see Eq. 6.9), a difference of up to 80 % between the anion and the
cation concentration (cf. Fig. 6.9) would be the result. This was not considered as a
reasonable approach for the evaluation of the experimental results. Still, one has to be
aware that hydrolysis occurs as indicated by the pH decrease.

mH3 O+ = 2 ⋅ mH2 SO4


= 2 ⋅ mM g(OH)2
mtotal (M g) = manalyzed (M g) + mHydrolysis (M g)
= manalyzed (M g) + m(M g(OH)2 )
= manalyzed (M g) + 0.5 ⋅ m(H2 SO4 )
= manalyzed (M g) + 0.5 ⋅ 10−pH (6.9)

The actual experimental data containing temperature, pressure, pH and magnesium


concentration can be found in Table D.3; the parameters for Eq. 6.3 for MgSO4 can be
found in Table 6.1. In contrast to the results on the phosphate salts, each data point
represents one sample. Thereby, the accuracy of the measurement is lower.

- 143 -
Chapter 6 ∥ Phosphate and sulfate salts

Figure 6.8 ∥ Solubility of MgSO4 as a function of density; ○, this work; dashed line
represents the description of the experimental data with Eq. 6.3

Table 6.1 ∥ Model parameters of the salts MgSO4 , Na2 HPO4 and NaH2 PO4 for Eq.
6.3

Salt ∆H/J ⋅ mol−1 ∆S/J ⋅ mol−1 ⋅ K −1 n/-


MgSO4 -8257 -154.4 3.31
Na2 HPO4 -142411 -351.4 5.37
NaH2 PO4 -35582 -152.4 3.47
KH2 PO4 -84569 -271.2 4.33

6.5 Conclusions
In the course of this work, the solubilities of the sulfate salts MgSO4 and CaSO4 in a
range of 18.8 - 23.2 M P a and 655 - 675 K as well as of the phosphate salts Na2 HPO4 ,
NaH2 PO4 and CaHPO4 in a range of 20.5 - 24.2 M P a and 665 - 690 K were investi-
gated. It has been found that experiments with CaSO4 and CaHPO4 lead to plugging
of the equipment with the current configuration of the setup due to low solubilities even
at a subcritical state. Therefore, no solubility data can be presented at this point for
these salts.
For the other salts, experiments have been conducted successfully. Here, deviations

- 144 -
6.5 ∥ Conclusions

(a)

(b)

Figure 6.9 ∥ Solubility of magnesium and sulfate (a) and comparison of sulfate concen-
tration and possible correction (b) as function of density for the experiments of MgSO4 ;
○ corresponds to sulfate concentration; △ corresponds to magnesium concentration; ◻
corresponds to corrected magnesium concentration

between the anion and cation concentrations occurred due to a parallel hydrolysis re-
action. These could partly be corrected by inclusion of the measured pH values. The
extent of the hydrolysis depends on the temperature and pressure during the experiments
and the investigated compound as found in previous articles of the authors (24; 25). The
results of the experiments were correlated with a semi-empirical model. This correlation
showed a good coincidence between experiments and proposed model.

- 145 -
Chapter 6 ∥ Phosphate and sulfate salts

For a better understanding of the behavior of phosphate salts in supercritical water,


more experiments with further salts and different conditions have to be conducted due
to the complexity (pH dependency, equilibria between different stages) of the phosphate
system.

6.6 Acknowledgements
The authors would like to thank the analytical team of Wetsus for their contribution in
the analysis of the samples.
This work was performed in the TTIW-cooperation framework of Wetsus, centre of
excellence for sustainable water technology (www.wetsus.nl). Wetsus is funded by the
Dutch Ministry of Economic Affairs, the European Union Regional Development Fund,
the Province of Fryslân, the City of Leeuwarden, and the EZ/Kompas program of the
’Samenwerkingsverband Noord-Nederland’. The authors like to thank the participants
of the research theme Salt for their financial support.

6.7 References
[1] S. Stucki, F. Vogel, C. Ludwig, A. G. Haiduc, M. Brandenberger, Catalytic gasification of algae
in supercritical water for biofuel production and carbon capture, Energy & Environmental Science
2 (5) (2009) 535–541.
[2] G. Brunner, Near critical and supercritical water. Part I. Hydrolytic and hydrothermal processes,
The Journal of Supercritical Fluids 47 (3) (2009) 373.
[3] T. J. Park, J. S. Lim, Y. W. Lee, S. H. Kim, Catalytic supercritical water oxidation of wastewater
from terephthalic acid manufacturing process, The Journal of Supercritical Fluids 26 (3) (2003)
201–213.
[4] M. D. Bermejo, M. J. Cocero, Supercritical water oxidation: A technical review, AIChE Journal
52 (11) (2006) 3933–3951.
[5] E. Lester, P. Blood, J. Denyer, D. Giddings, B. Azzopardi, M. Poliakoff, Reaction engineering: The
supercritical water hydrothermal synthesis of nano-particles, The Journal of Supercritical Fluids
37 (2) (2006) 209.
[6] Y. Hakuta, H. Ura, H. Hayashi, K. Arai, Effects of hydrothermal synthetic conditions on the
particle size of γ-AlO(OH) in sub- and supercritical water using a flow reaction system, Materials
Chemistry and Physics 93 (2-3) (2005) 466.
[7] A. Kruse, E. Dinjus, Hot compressed water as reaction medium and reactant: Properties and
synthesis reactions, The Journal of Supercritical Fluids 39 (3) (2007) 362.
[8] P. E. Savage, A perspective on catalysis in sub- and supercritical water, The Journal of Supercritical
Fluids 47 (3) (2009) 407.
[9] D. E. Knox, Solubilities in supercritical fluids, Pure Applied Chemistry 77 (2005) 513 – 530.
[10] T. Clifford, Fundamentals of Supercritical Fluids, Oxford University Press, 1999.
[11] F. J. Armellini, J. W. Tester, G. T. Hong, Precipitation of sodium chloride and sodium sulfate
in water from sub- to supercritical conditions: 150 to 550 ○ C, 100 to 300 bar, The Journal of
Supercritical Fluids 7 (3) (1994) 147.

- 146 -
6.7 ∥ References

[12] M. Hodes, P. Griffith, K. A. Smith, W. S. Hurst, W. J. Bowers, K. Sako, Salt solubility and
deposition in high temperature and pressure aqueous solutions, American Institute of Chemical
Engineers Journal 50 (2004) 2038 – 2049.
[13] M. Hodes, P. A. Marrone, G. T. Hong, K. A. Smith, J. W. Tester, Salt precipitation and scale
control in supercritical water oxidation – part A: Fundamentals and research, The Journal of
Supercritical Fluids 29 (3) (2004) 265.
[14] P. A. Marrone, M. Hodes, K. A. Smith, J. W. Tester, Salt precipitation and scale control in super-
critical water oxidation–part B: Commercial/full-scale applications, The Journal of Supercritical
Fluids 29 (3) (2004) 289.
[15] A. Kruse, Hydrothermal biomass gasification, The Journal of Supercritical Fluids 47 (3) (2009)
391–399.
[16] P. A. Marrone, G. T. Hong, Corrosion control methods in supercritical water oxidation and gasi-
fication processes, The Journal of Supercritical Fluids 51 (2) (2009) 83–103.
[17] G. Brunner, Near and supercritical water. Part II: Oxidative processes, The Journal of Supercritical
Fluids 47 (3) (2009) 382.
[18] M. Schubert, J. W. Regler, F. Vogel, Continuous salt precipitation and separation from supercritical
water. Part 1: Type 1 salts, The Journal of Supercritical Fluids 52 (1) (2010) 99–112.
[19] K. Prikopsky, B. Wellig, P. R. von Rohr, SCWO of salt containing artificial wastewater using a
transpiring-wall reactor: Experimental results, The Journal of Supercritical Fluids 40 (2) (2007)
246.
[20] B. Kruse, D. Forchheim, F. Ottinger, J. Zimmermann, Alkali salts in hydrothermal biomass gasi-
fication: chance and challenge, Proceedings of the 9th International Symposium on Supercritical
Fluids.
[21] M. Schubert, J. W. Regler, F. Vogel, Continuous salt precipitation and separation from supercritical
water. Part 2: Type 2 salts and mixtures of two salts, The Journal of Supercritical Fluids 52 (1)
(2010) 113–124.
[22] G. Tchobanoglous, F. L. Burton, H. D. Stensel, Wastewater engineering: treatment and reuse,
McGraw-Hill Science Engineering, 2003.
[23] I. Leusbrock, S. Metz, G. Rexwinkel, G. F. Versteeg, Quantitative approaches for the description
of solubilities of inorganic compounds in near-critical and supercritical water, The Journal of
Supercritical Fluids 47 (2) (2008) 117–127.
[24] I. Leusbrock, S. J. Metz, G. Rexwinkel, G. F. Versteeg, Solubility of 1:1 alkali nitrates and chlorides
in near-critical and supercritical water, Journal of Chemical & Engineering Data 54 (12) (2009)
3215–3223.
[25] I. Leusbrock, S. J. Metz, G. Rexwinkel, G. F. Versteeg, The solubility of magnesium chloride and
calcium chloride in near-critical and supercritical water, accepted for publication in The Journal
of Supercritical FluidsDOI: 10.1016/j.supflu.2009.12.015.
[26] W. T. Wofford, P. C. Dellorco, E. F. Gloyna, Solubility of potassium hydroxide and potassium
phosphate in supercritical water, Journal of Chemical and Engineering Data 40 (4) (1995) 968–
973.
[27] J. Chrastil, Solubility of solids and liquids in supercritical gases, Journal Of Physical Chemistry
86 (15) (1982) 3016–3021.
[28] R. E. Mesmer, W. L. Marshall, D. A. Palmer, J. M. Simonson, H. F. Holmes, Thermodynamics
of aqueous association and ionization reactions at high-temperatures and pressures, Journal of
Solution Chemistry 17 (8) (1988) 699–718.
[29] W. Wagner, The IAPWS formulation 1995 for the thermodynamic properties of ordinary water
substance for general and scientific use, Journal of Physical and Chemical Reference Data 31 (2)
(1999) 387.
[30] D. R. Ride, CRC Handbook of Chemistry and Physics, CRC Press, 2004.
[31] P. Dell’Orco, H. Eaton, T. Reynolds, S. Buelow, The solubility of 1:1 nitrate electrolytes in
supercritical water, The Journal of Supercritical Fluids 8 (3) (1995) 217.

- 147 -

You might also like