Joachim
Reimer
a and
Frédéric
Vogel
*ab
aPaul Scherrer Institute, Laboratory for Bioenergy and Catalysis, OVGA/104, CH-5232 Villigen PSI, Switzerland. E-mail: Frederic.vogel@psi.ch; Fax: +41 56 3102199; Tel: +41 56 3102135
bFachhochschule Nordwestschweiz, 5210 Windisch, Switzerland
First published on 3rd October 2013
Aqueous salt solutions under hydrothermal conditions play an important role in geochemistry as well as in processes using hot compressed water as the process medium such as supercritical water oxidation (SCWO) and supercritical water gasification (SCWG). Isochoric high pressure differential scanning calorimetry (HP-DSC) was used as an accurate technique to investigate the phase behavior of such solutions under hydrothermal conditions. New data in the low concentration range (0.14–15.0 mass%) has been collected for the binary systems K2SO4–H2O, Na2SO4–H2O and K2HPO4–H2O. Furthermore we have discovered a liquid–liquid immiscibility in the ternary system K2SO4–Na2SO4–H2O, which has not been reported before.
At the Paul Scherrer Institute a hydrothermal gasification process was developed to produce methane from wet biomass.5 Inorganic compounds in the biomass feedstock can cause problems in the process by poisoning the methanation catalyst or lead to a blocking due to precipitation of solid salt at supercritical conditions. Therefore the inorganic salts have to be removed from the feed stream. Furthermore the separation of inorganic salts from the feed stream opens the possibility to recover nutrients such as phosphorus, potassium and ammonia, which could again be used as fertilizer in biomass production.
To optimize this salt separation process a detailed knowledge of the phase behavior of salt solutions is needed.
Historically, binary phase diagrams of aqueous salt solutions were divided into two major groups. The first group (type 1) has a continuous solubility line from the triple point of pure water to the triple point of the pure salt. Salts with type 1 behavior include e.g. halides and nitrates. The second group (type 2) is characterized by a solubility line that intersects the critical line in a lower critical endpoint p and a higher critical endpoint q. Between those invariant points the fluid is in equilibrium with the solid salt phase. Typical type 2 salts are sulfates, carbonates, silicates and oxides. Often phase diagrams of both types are complicated by liquid–liquid immiscibilities. Valyashko derived a set of phase diagrams for all possible cases.6
Aqueous Na2SO4 and K2SO4 solutions are known to have a phase diagram of type 2d′ (ref. 7) which possesses a metastable liquid–liquid immiscibility. K2HPO4–H2O is known for its type 1d behavior exhibiting a stable liquid–liquid immiscibility below the liquid 1-gas critical endpoint R.7 The schematic T–x projections of the two phase diagrams of interest (type 1d, 2d′) are shown in Fig. 1.
Fig. 1 T–x projections of type 1d and 2d′ schematic phase diagrams. Bold lines – liquid composition at the three phase equilibrium (G–L–S and G–L1–L2); dashed lines – gas phase composition at the three phase equilibrium (G–L–S and G–L1–L2); dash-dotted lines – critical curves; dotted lines – metastable liquid–liquid immiscibility. EG – composition of gas phase at eutectic equilibrium (G–L–SW–SS); EL – composition of liquid phase at eutectic equilibrium (G–L–SW–SS); TPW, TPS – triple point of pure water and pure salt, respectively; CPW, CPS – critical points of pure water and pure salt, respectively; N – lower critical end-point (L1 = L2–G); R – upper critical end-point (L1 = G–L2); p, q – critical end-points (G = L–SS). Adapted from Valyashko.6 |
As in naturally occurring salt solutions typically more than one salt is dissolved, higher order mixtures are also of interest. In the phase diagrams of such solutions the properties of one binary mixture transform into the properties of the second binary mixture, and this leads to either continuous critical lines or invariant critical endpoints.6 Valyashko also developed a system to classify these phase diagrams.6 The ternary system K2SO4–Na2SO4–H2O was studied up to 200 °C by Freyer and Voigt8 who reported the formation of the double salt Glaserite of the formula NaK3(SO4)2 in certain concentration ranges, also with varying Na:K ratios.
In earlier investigations from our group9–11 the continuous salt separation from hydrothermal salt solutions was investigated. Binary type 1 salt solutions showed high separation efficiencies, whereas type 2 solutions showed low separation efficiencies and caused deposition of solid salt in the apparatus. Interestingly, a ternary solution of the two type 2 salts Na2SO4 and K2SO4 could also be recovered efficiently. The salt deposition in the salt separation unit was studied with neutron radiography on the macro-scale.12–14 The salt precipitation and separation in connection with SCWG and SCWO processes was also studied in other groups using different approaches e.g. precipitation on a hot finger, special reactor designs (e.g. MODAR reactor, transpiring wall reactor).2,3,15–21 The results of these studies are often affected by the design of the used setup and restricted to the range of the parameters (p, T, x) varied.
For a better understanding of the phase behavior of salt solutions we used differential scanning calorimetry as a thermal analysis tool to investigate the phase transitions in such solutions. Thermal analysis is a sensitive and accurate tool to investigate phase transitions and phase behavior.22,23 Differential Scanning Calorimetry (DSC) is very sensitive towards phase transitions accompanied by changes in the heat capacity of the sample. The DSC measures the heat flow into or out of the sample versus a reference. Changes in the heat capacity of the sample due to phase transitions lead to step or peak shaped signals in the heat flow curves. The measured heat flow is proportional to the sample mass, the heating/cooling rate and the specific heat capacity (cV) of the sample (eqn (1)) and in addition to that affected by an instrumental baseline.
Φmeasured = Φsample + Φbaseline = cvmβ + Φbaseline | (1) |
As a result of this relation the signal intensity increases with high scanning rates, but often smaller thermal effects vanish at such high rates due to intense broad signals of stronger effects. This led to problems in the interpretation of the heat flow curves in earlier investigations in our group24 where a very high scanning rate of 10 K min−1 had been chosen.
To test the method for accuracy we first measured salt solutions of Na2SO4, which have been studied extensively before.25–35 For K2SO4 and K2HPO4 much less data is available in the literature. Subsequently, measurements above 200 °C on the ternary system Na2SO4–K2SO4–H2O were performed.
The salt solutions were prepared gravimetrically with an accuracy of ±0.1 mg and then weighed into the Incoloy crucibles with the same accuracy. Deionized water and salts with a purity >99.5% were used for the sample preparation. The crucibles are rated up to 50 MPa at 600 °C. The inner volume of the crucibles was determined to be 128.63 ± 0.54 μL (95% confidence interval) by fully filling them with water at 25 °C and weighing.
The crucibles were filled with 38.6 ± 0.1 mg of the liquid sample, and therefore the average density was 300 ± 1 kg m−3. An empty crucible was used as reference.
During the measurement the sensor was flushed with 20 mL min−1 of argon. The heating rate was 10 K min−1 for the heat-up phase. After an isothermal step of 1 h the measurement started with a heating/cooling rate of 0.1 K min−1.
The experimental data was treated with the Calisto Software (AKTS, Switzerland). Typically a smoothing of 25–50 points was necessary. Multiple measurements were performed to determine the uncertainty of the measurement.
The differences in the isochoric heat capacity (ΔcV) of the samples before and after a phase transition were determined using the glass transition tool of the Calisto software. This tool constructs tangents to the heat flow curves before and after a step-shaped transition and then calculates the ΔcV from the intersection points of those tangents with a tangent on the inflection point of the curve using the following relation (eqn (2)):
(2) |
Fig. 2 Comparison of the heat flow signals in heating and cooling mode at 0.1 K min−1, 6.69 mass% Na2SO4, average density 300 kg m−3. |
From the transition temperatures a part of the phase diagram can be constructed by correcting the concentration of the liquid phase with the method proposed by Valyashko et al.35 using the density data from Khaibullin and Novikov.29 This correction is needed because water evaporates from the starting solution during heating and therefore the salt concentration in the liquid phase increases. Concentrations of the salt in the vapor phase are normally very small compared to the concentration in the liquid phase and were thus neglected here.
The thermal expansion of the crucible was calculated from the material constants. The expansion of the crucibles due to pressure changes were taken into account. Furthermore we relied on the vapor density data available in the literature and did not use any data on the vapor density from databases or calculations. The uncertainties for the liquid concentration were estimated by calculation of the liquid concentration for extreme values of the liquid and vapor density, as proposed by Valyashko et al.35
Our corrected measurements are presented in Table 1. A comparison with literature data is shown in Fig. 3. The data obtained from the DSC measurements is in excellent accordance with the literature data. The metastable liquid–liquid immiscibility has not been observed. This is in accordance with Valyashko et al.35 suggesting the immiscibility to be suppressed by the appearance of the solid phase.
Initial concentration/mass% | T/°C (G–L–S) | Liquid solution | Vapor solution | |
---|---|---|---|---|
x/mass% | ρ/kg m−3 | ρ/kg m−3 | ||
a Obtained from interpolation of data from Khaibullin and Novikov.29 | ||||
0.140 | 372.4 ± 0.1 | 0.260 ± 0.005 | 435 ± 2a | 214 ± 2a |
0.696 | 360.7 ± 0.2 | 1.02 ± 0.01 | 540 ± 2a | 148 ± 2a |
1.39 | 352.5 ± 0.2 | 1.86 ± 0.02 | 594 ± 2a | 120 ± 2a |
2.75 | 342.2 ± 0.1 | 3.47 ± 0.02 | 652 ± 2a | 95.7 ± 2a |
6.69 | 326.6 ± 0.3 | 7.96 ± 0.05 | 755 ± 2a | 70.6 ± 2a |
15.0 | 305.7 ± 0.1 | 17.1 ± 0.1 | 884 ± 2a | 50.5 ± 2a |
Fig. 3 Temperature–composition plot for the liquid at the three-phase equilibrium (G–L–S) of the system Na2SO4 + H2O. |
Initial concentration/mass% | T/°C (G–L–S) | Liquid solution | Vapor solution | |
---|---|---|---|---|
x/mass% | ρ/kg m−3 | ρ/kg m−3 | ||
a Obtained from extrapolation of data from Puchkov et al.36 b Obtained from extrapolation of the vapor pressures from Ravich et al.37 and calculation by the NIST Chemistry Webbook.38 | ||||
0.864 | 371.7 ± 0.2 | 1.69 ± 0.03 | 565 ± 2a | 196 ± 2b |
1.72 | 367.7 ± 0.1 | 2.90 ± 0.04 | 586 ± 2a | 173 ± 2b |
3.40 | 362.3 ± 0.6 | 5.19 ± 0.05 | 615 ± 2a | 148 ± 2b |
5.04 | 358.9 ± 0.1 | 7.34 ± 0.07 | 639 ± 2a | 137 ± 2b |
8.19 | 353.5 ± 0.1 | 11.4 ± 0.1 | 691 ± 2a | 121 ± 2b |
Our results are in good accordance with the few data sets available in the literature (Fig. 4), especially with the data of Ravich and Borovaya.39 Further measurements of densities are required to improve the correction of the measured DSC data. The DSC measurements also showed substantial superheating in this system, therefore all data was measured in the cooling mode.
Fig. 4 Temperature–composition plot for the liquid at the three-phase equilibrium (G–L–S) of the system K2SO4 + H2O. |
Initial concentration/mass% | T/°C (G–L1–L2) |
---|---|
0.434 | 376.7 ± 0.1 |
0.865 | 374.8 ± 0.1 |
1.72 | 371.4 ± 0.1 |
3.96 | 366.6 ± 0.1 |
6.46 | 364.2 ± 0.2 |
As in the measurements with the sulfate solutions the λ-shape of the second transition was less distinct in the heating mode compared to the cooling mode.
No phase density data is available in the literature for this system and therefore the correction for the liquid phase concentration could not be applied. Comparing our measurements to those of Marshall et al.,40,41 which were also taken at isochoric conditions, but probably at higher densities, we see a consistent trend of the data points (Fig. 5). This is especially the case if we assume that all data points in this study have to be corrected to higher concentrations.
Fig. 5 Temperature–initial composition plot for the liquid at the three-phase equilibrium (G–L1–L2) of the system K2HPO4 + H2O. |
Fig. 6 Comparison of the heat flow curves of a K2HPO4 (6.46 mass%) solution and a Na–K SO4 (1:1) solution. |
Initial concentration (Na2SO4)/mass% | Initial concentration (K2SO4)/mass% | Molar ratio K:Na | T/°C (G–L1–L2) | T/°C (G–L) |
---|---|---|---|---|
0.699 | 1.71 | 2:1 | 367.79 ± 0.07 | 376.93 ± 0.03 |
1.40 | 0.857 | 1:2 | 363.20 ± 0.06 | 376.25 ± 0.01 |
1.39 | 1.70 | 1:1 | 363.54 ± 0.07 | 376.52 ± 0.02 |
0.688 | 3.38 | 4:1 | 367.09 ± 0.01 | 376.99 ± 0.01 |
The immiscibility may arise through the metastable states which are reported for the binary solutions of sodium and potassium sulfate. A similar effect has been reported for the system K2SO4–Li2SO4–H2O.42–44 This liquid–liquid immiscibility was observed at all molar ratios K:Na from 1:2 to 4:1.
G | Gas/vapor phase |
L | Liquid phase |
S | Solid phase |
F | Supercritical fluid |
c V | Isochoric specific heat capacity |
Φ | Heat flow |
β | Heating rate |
m | Sample mass |
This journal is © The Royal Society of Chemistry 2013 |