Salting-Out Crystallisation Using NH3 in a

Laboratory-Scale Gas Lift Reactor

D. H. Jenkins*
CSIRO Minerals, Box 312, Clayton South, Victoria 3169, Australia

Despite the advantages offered by gas lift reactors with respect to high gas–liquid mass transfer with a low energy input, their acceptance in the
crystallisation field has been slow, especially on an industrial scale. Potassium chloride, potassium sulfate, and magnesium chloride hexammoniate
(MgCl2 ·6NH3 ) were crystallised in a laboratory-scale gas lift crystalliser by salting-out using ammonia gas. Ammonia mass transfer rates were
calculated for each test. To achieve maximum crystal growth, the gas rate in these reactors needs to be optimised for each crystallising system to
achieve sufficient gas mass transfer as well as providing sufficient crystal slurry agitation.

Malgré les avantages offerts par les réacteurs à injection de gaz par rapport au transfert de masse gaz-liquide élevé avec un faible apport d’énergie,
leur acceptation dans le domaine de la cristallisation est lente, particulièrement à l’échelle industrielle. On a cristallisé le chlorure de potassium, le
sulfate de potassium et l’hexammoniate de chlorure de magnésium (MgCl2 ·6NH3 ) dans un cristalliseur à injection de gaz à l’échelle laboratoire par
relargage au moyen d’un gaz ammoniac. On a calculé les vitesses de transfert de masse ammoniaque pour chaque essai. Pour avoir une croissance
cristalline maximale, il est nécessaire d’optimiser la vitesse du gaz dans ces réacteurs pour chaque système de cristallisation afin d’obtenir un
transfert de masse de gaz suffisant tout en assurant une agitation de bouillie cristalline suffisante.

Keywords: crystal growth, crystallisation, gas lift reactor, mass transfer

INTRODUCTION additional component is a gas, the agitator also has to ensure high
gas–liquid mass transfer.

C
rystallisation offers a higher degree of purification in a sin-
Often the gases used in salting-out reactions have a high solu-
gle step than any other process and in many cases is the
bility and in dilute solution the liquid film resistance is very small.
simplest and cheapest means of obtaining a pure substance
However, as the concentration increases the liquid film resistance
from an impure solution (Mullin, 1992). A variety of crystalliser
will increase and dissolution will be slower. Therefore, to give
designs have been proposed to maintain the super-saturation lev-
the entering soluble gas a higher chance of being absorbed, these
els constant throughout the crystalliser and to ensure that the
crystallisers often have a large height to diameter ratio (Fernandez
crystal slurry is well mixed and suspended (Mersmann and Ren-
Lozano and Wint, 1980).
nie, 1995). This agitation in the crystalliser has the propensity to
Gas lift reactors (GLRs) are important for aerobic fermenta-
damage and abraid the crystals resulting in a smaller crystal size
tions as well as in wastewater treatment on account of their
distribution due to the formation of secondary nuclei (Neumann
simple construction and low energy consumption (The Chemical
et al., 1999).
Engineer, 1987). In GLRs the contents are pneumatically agitated
In some crystallising systems the method of inducing super-
saturation is by introducing a third component into the system
(Jenkins and Sinha, 1983; Elsner et al., 1984; Sheehan et al.,
∗ Author to whom correspondence may be addressed.
1995). These salting-out procedures have the common difficulty
E-mail address: dhands1jenkins@bigpond.com
that the point at which the additional component is introduced is
Can. J. Chem. Eng. 87:869–878, 2009
highly super-saturated and spontaneous nuclei are likely to form
before the additive is evenly dispersed (Jones, 1991). Where the
© 2009 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.20220

| VOLUME 87, DECEMBER 2009 | | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 869 |
by a stream of air or other gases, and this stream also has the
Table 1. Dimensions of laboratory gas lift crystalliser
important function of mass transfer between the gas phase and
liquid phase. GLRs present high gas–liquid mass transfer with a
Total volume (dm3 ) 1.785
low energy input, have defined liquid flow patterns, and can be
easily controlled. GLRs are low shear stress type reactors, which Operating volume (dm3 ) 1.595
has hastened their acceptance in the bioreactor field due to the
high shear sensitivity of many microorganisms. Disengagement volume (dm3 ) 0.458
Therefore, GLRs may be an option for gas salting-out reactions
Riser volume (dm3 ) 0.946
especially for crystals that are soft and friable. Despite the advan-
tages offered by GLRs their acceptance in the crystallisation field Downcomer volume (dm3 ) 0.381
has been slow, especially on an industrial scale. Pilot scale crys-
tallisation of Ca(CO)3 in a draft-tube fluidising bed reactor has Diameter of riser (m) 4.65 × 10−2
been described by Jones et al. (1992) and Rigopoulos and Jones
(2003), while gas–liquid mass transfer characteristics were deter- Diameter of downcomer (m) 3.00 × 10−2
mined by Sada et al. (1985) in a bubble column containing slurries
Heat exchanger (H/E, m2 ) 0.05
of fine calcium hydroxide. Recently, Bao et al. (2001) developed
a kinetic model for the production of calcium gluconate crystals AD :AR excluding H/E 0.40
using external loop airlift bubble columns. This was followed by
experimental work to verify these optimised operating conditions AD :AR including H/E 0.24
(Arimatsu et al., 2004). AD , area of downcomer; AR , area of riser.

Characteristics of GLRs
In crystallisation, all particles need to be suspended in the mother in the downcomer above the heat exchanger and entered the
liquor to provide the maximum possible surface area for homoge- crystalliser through a 4-mm ID tube via a stopcock as shown in
nous conditions of mass transfer from the liquid to the solid phase. Figure 1. This point was selected to ensure that the feed was well
Zwietering (1958) defined the just suspended speed and the just mixed prior to combining with the crystallising gas. The gas used
suspended power applied by the agitator in stirred tanks. This is to promote both circulations within the crystalliser and to effect
the minimum impeller speed (and power needed) at which no
particle remained static on the vessel base.
In GLRs, both the agitation and the mass transfer functions are
supplied by the incoming gas. Therefore in a similar manner, there
should be a minimum power supplied by the bubbling gas to
ensure that the particles are suspended. Both Miller (1974) and
Bhavaraju et al. (1978) give the power supplied by the bubbling
gas in a GLR.
In terms of mass transfer, gas holdup, εGR , is an important
parameter because it determines the amount of the gas phase
retained in the system at any time (Merchuck, 1990). The gas
holdup also promotes liquid circulation, which in a gas lift crys-
talliser depends on the interaction between the gas and solid
holdups in the riser which are dependent on the solid and liq-
uid properties. Generally, correlations for the gas holdup involve
the gas superficial velocity, the cross-sectional areas of both the
downcomer and the riser, and the effective viscosity of the liquid.

EXPERIMENTAL DETAILS
Apparatus
The gas lift crystalliser, used in this work, was based on a design
for a photo bioreactor used for the continuous culture of Spir-
ulina platensis (Vernerey et al., 2001). The glass external loop
gas lift crystalliser contained a cooling coil, in a similar position
to the heat exchanger in the 1,2-ethylene dichloride bubble col-
umn reactor of Orejas (1999) to control the reaction temperature.
The reactor also contained a gas sparging point, a feed inlet, and
a crystal slurry outlet while a thermocouple inserted in a glass
thermo-well measured the temperature in the riser section of the
crystalliser. The dimensions and capacities of the laboratory gas
lift crystalliser are shown in Table 1.
During operation of the crystalliser, cooling water was circu-
lated between a water bath and the crystalliser cooling coil by a
small centrifugal pump. The feed to the crystalliser was admitted Figure 1. Schematic diagram of laboratory scale gas lift crystalliser.

| 870 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 87, DECEMBER 2009 |
the crystallisation was admitted via a sparger at the base of the
riser.
Two types of sparger were used in the crystalliser. For most tests
the sparger used contained two 1 mm holes 180◦ apart. However,
a sparger similar to the feed tube with a single 3 mm diameter
hole was used for the crystallisation of KCl as the smaller feed
holes in the sparger rapidly blocked with crystals due to the high
local super-saturation at the holes in this system.
Crystallisation Experiments
Prior to the commencement of a test, the cooling water was circu-
lated between the heat exchanger in the crystalliser and the water
bath. The water bath was set approximately 2◦ below the crys-
talliser operating temperature. Liquid was added to the crystalliser
prior to the introduction of ammonia. This liquid was glycol for
the two hexammoniate crystallisation tests (Sheehan et al., 1995)
and H2 O, the usual solvent, for the inorganic salt K2 SO4. A dilute
NaCl/KCl solution was used for the KCl tests due to the higher
solubility of these species in the ammonia/water system. These
solutions were then saturated with NH3 at the respective crys-
tallising temperatures. For MgCl2 ·6NH3 this was 50◦ C, while for
K2 SO4 and KCl it was 40 and 30◦ C, respectively.
To avoid freezing of the feed for the hexammoniate crystalli-
sation tests, the solution has to be kept at a temperature of
approximately 120◦ C. The hot feed was pumped from the Schott
bottle into the crystalliser at approximately 20 g/min. The feed for
the K2 SO4 and the KCl tests was fed to the crystalliser at a similar
rate but at ambient temperature, which was approximately 20◦ C.
The duration of the tests varied between 468 min for the KCl
test and 655 min for the hexammoniate test. During the tests
small samples of crystal slurry were removed from the crystalliser,
filtered through a 0.45-␮m syringe filter, and made up to 100 mL
volume for chemical analysis. Each solution was analysed for the
major components as well as ammonia.
Three larger crystal slurry samples were removed from each
test for crystal sizing. Prior to taking these samples the gas flow
rate into the crystalliser was increased to circulate any settled
crystals between the downcomer and the riser. The slurry sam-
ples were centrifuged using a laboratory basket centrifuge and
the crystals washed on the centrifuge with ammonia-saturated
methanol. A sub-sample of the washed crystals was used for crys-
tal sizing while an X-ray diffraction (XRD) scan was completed
on a second sample to identify the crystal phase.
Crystal Sizing
All samples of the washed, damp crystals were first dried by
passing ammonia gas through an up-flow drying tube containing
approximately 30 g of crystals and fluidising them for approxi-
mately 30 min.
The dried crystals were split using a riffle to give a sub-sample
of approximately 15 g. This sub-sample was transferred to the top
screen in the stack (500 ␮m), which had previously been flushed
with dry nitrogen and taped together. After shaking the screens
for 30 min, the screens were separated in a glove box and each
fraction transferred to pre-weighed sample bottles. The sample
bottles with each screen fraction were re-weighed and the crystal
size distribution calculated.
Analytical Procedures
Ammonia
Ammonia analyses were determined using a Tecator 1035 Auto-
matic Kjeltec Analyser. During calibration, recovery figures
| VOLUME 87, DECEMBER 2009 | |
between 99.5% and 100.2% were obtained when using AR grade
dried NH4 Cl.
Magnesium, sodium, and potassium
At completion of the experiments, the filtered liquid or solid was
dissolved in de-ionised water containing 10 mL of 6 M HNO3 and
the solution was made up to 100 mL total volume. While the
reported magnesium results were determined by titration with
0.05 M EDTA solution, confirmatory analyses for all samples were
determined by ICP. Sodium, potassium, and sulfate were also
determined using a Varian Vista ICP.
X-ray diffraction
XRD scans were completed on all solid samples. While KCl and
K2 SO4 were not affected by the moisture in the air, hexammoniate
rapidly absorbed moisture so the samples need to be covered dur-
ing the scans. These samples were placed in a sample holder and
covered by plastic cling wrap, which was transparent to X-rays
over the 2 range used.
Patterns were collected on a Philips PW1710 powder diffrac-
tometer, fitted with a diffracted beam graphite monochromator
using CuK˛ radiation. The scanning rate of the diffractometer was
set at 0.08◦ 2/s at 40 kV and 40 mA. Total scan times were of the
order of 12 min per sample.
RESULTS AND DISCUSSION
Crystallisation Tests
Magnesium chloride hexammoniate
Figure 2 shows a sample of MgCl2 ·6NH3 crystals produced from
a laboratory scale, semi-continuous stirred vessel test at 50◦ C.
This figure indicates that the hexammoniate crystals were mainly
agglomerates although they were well faceted.
The hexammoniate crystals produced from the initial gas
lift crystallisation test, also at 50◦ C, are shown in Figure 3.
The rounded crystals produced using the gas lift crystalliser
suggest that hexammoniate crystals are soft or brittle and that
crystal–crystal and crystal–crystalliser contact rounded the
crystals. The rounding of these hexammoniate crystals is similar
to the rounding exhibited by NaCl from crystallisers with external
heat exchangers and forced circulation (van Damme, 1973). Mers-
mann (1995) also indicated that rounding of KNO3 can occur.
Observations of many previous laboratory scale, semi-continuous
Figure 2. Hexammoniate crystals produced in stirred batch
crystallisation test at 50◦ C (32×). [Colour figure can be viewed in the
online issue, which is available at www.interscience.wiley.com.]
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 871 |
 Table 2. MgCl2 , NH3 levels, and crystal yield during GLR
hexammoniate crystallisation tests at 50◦ C

Time (h) MgCl2 (%) NH3 (%) Yield (%)

MgCl2 ·6NH3 crystallisation test number 1

0.5 3.27 8.95 74.7

1 3.07 8.87 76.7

2 2.93 8.91 77.8

3 2.71 9.06 79.4

4 2.68 8.99 79.7

Figure 3. Hexammoniate crystals produced in the initial gas lift reactor
test at 50◦ C (32×). [Colour figure can be viewed in the online issue, 5 2.79 8.97 78.8
which is available at www.interscience.wiley.com.]
6 2.79 9.00 79.1

7 2.73 9.10 79.5

8 2.75 8.91 79.4

9 2.85 8.97 78.6

10 2.82 8.98 78.8

MgCl2 ·6NH3 crystallisation test number 2

0.38 2.54 8.78 83.6

0.98 3.12 8.42 79.8

1.97 3.12 8.21 79.8

3.05 3.20 8.49 79.2

Figure 4. XRD scans of hexammoniate crystals shown in Figures 2 and 3. 4.03 3.02 8.80 80.4
[Colour figure can be viewed in the online issue, which is available at
www.interscience.wiley.com.] 4.97 2.94 8.85 80.9

stirred vessel hexammoniate tests, where agglomerates were 6.47 3.37 8.48 78.2
always produced, suggest that despite rounding, the hexammo-
niate crystals shown in Figure 3 are also agglomerates. Kotaki 7.13 3.79 8.31 75.4
and Tsuge (1990) in their work on the crystallisation of calcium
8.13 3.30 8.64 78.6
carbonate suggest that agglomeration is a consequence of high
crystal suspension density. 9.13 3.56 8.36 77.0
XRD scans shown in Figure 4 indicated that hexammoniate
was produced in both tests despite the difference in crystal 10.21 3.49 8.78 77.3
morphology.
The MgCl2 content of the feed solutions used in the two hex-
ammoniate tests was 13.0% and 14.9% in glycol, respectively. cubic shape as Figure 5 indicates. This was in contrast to the
Table 2 shows the MgCl2 content, the NH3 content, and the elongated shape shown in the larger crystals produced by Budz
crystal yield achieved in these tests. et al. (1987).
While the MgCl2 in the feed for test number 1 was lower, the The K2 SO4 and NH3 content in the crystalliser and the crystal
higher NH3 level in the liquid phase for this test meant that the yield during the test are shown in Table 3. Here the crystal yield at
crystal yield was similar to that obtained from test number 2. For 40◦ C with a feed containing 10.18% K2 SO4 was over 95%, which
the second test, the lower NH3 concentration was compensated was slightly lower than the 99% yield achieved by Fernandez
for by the higher MgCl2 content in the feed. This meant that the Lozano and Wint (1979) at 15 and 20◦ C.
yields for both tests were approximately the same. The higher
NH3 saturation achieved in test number 1 was a consequence of Potassium chloride
the higher gas flow rate used in this test. Table 4 shows that the feed for the second KCl crystallisation test
contained a higher percentage of NaCl. This resulted in a lower
Potassium sulfate concentration of KCl in the barren liquor of the second test due to
Unlike the hexammoniate crystals, the K2 SO4 crystals produced the salting-out effect of the NaCl (see Tables 5 and 6). The results
in the gas lift crystalliser were not rounded but exhibited a of Gaska et al. (1965) indicated that the equilibrium level of KCl

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 Table 6. KCl, ammonia levels, and crystal yield (%) during KCl test
number 2 at 30◦ C

Time (h) KCl (%) NaCl (%) NH3 (%) KCl yield (%)

0 9.51 3.83 23.95 —

0.73 8.13 7.87 23.43 37.2

1.48 7.55 9.93 23.33 42.2

2.23 7.15 10.68 22.92 45.9

3.15 7.25 11.37 22.76 45.2

4.15 7.05 11.32 22.69 46.9

Figure 5. K2 SO4 crystals produced during gas lift reactor test at 40◦ C
(36×). 5.07 6.95 11.23 23.04 47.5

6.07 6.85 11.23 22.90 48.4

Table 3. K2 SO4 , NH3 , and crystal yield (%) during test at 40◦ C 7.07 6.94 11.34 23.18 47.5

8.35 6.89 11.31 23.16 47.9

Time (h) K2 SO4 (%) NH3 (%) Yield (%)

0.5 0.48 22.83 94.5

1.0 0.43 22.97 95.0

2.37 0.43 22.89 95.1

3.92 0.41 23.22 95.3

5.58 0.47 22.53 94.6

7.20 0.39 23.00 95.5

7.93 0.31 24.15 96.4

Table 4. Feed composition for KCl crystallisation tests Figure 6. KCl crystals produced during gas lift reactor test at 30◦ C with
50% excess NH3 (36×).
Feed sample number KCl (%) NaCl (%)

KCl number 1 17.65 10.95 in a solution containing 10% NaCl and 23% NH3 at 25◦ C was
approximately 5.5%. Given that the solubility of KCl in ammonia
KCl number 2 15.90 14.42 solution increases with temperature the solubilities and yields at
30◦ C, shown in Table 5 appear consistent with their results.
Like the crystals produced in the K2 SO4 test, the KCl crystals
also exhibit a cubic shape as Figure 6 indicates.
Table 5. KCl, ammonia levels, and crystal yield (%) during KCl test At 30◦ C, the yield of KCl in the initial test from the mixed
number 1 at 30◦ C chloride feed containing 11% NaCl varied between 45% and
51%. In the second test shown in Table 6, this increased to more
Time (h) KCl (%) NaCl (%) NH3 (%) KCl yield (%) than 47% at a corresponding lower NH3 level due to the higher
NaCl content in this feed depressing the KCl solubility. Higher
0 8.07 7.22 23.21 — yields in this system could be obtained at lower temperatures
0.75 7.97 8.13 23.42 45.8
however ammonia utilisation would be lower.

1.5 7.66 8.19 22.90 48.5 Ammonia Utilisation

In this test work, NH3 gas was needed to both promote circulation
2.42 7.58 8.47 23.19 48.9
throughout the crystalliser and also to produce the crystals at
4.32 8.16 9.00 23.72 44.1
the relevant saturation levels. To minimise the pumping power
needed for ammonia injection, the optimum ammonia rate should
5.78 7.30 8.60 23.53 50.8 be slightly in excess of that required to produce the relevant
saturation level. However, depending on the crystal density,
7.63 7.28 8.40 23.52 50.9 this ammonia rate may not produce the circulation necessary

| VOLUME 87, DECEMBER 2009 | | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 873 |
 Table 7. NH3 requirement and superficial gas velocity used in gas lift crystalliser tests

Crystal type Needed (g/min) Actual (g/min) Excess (%) Superficial velocity (m/s) Mass transfer (mol/s) Orifice Reo

Hex (1) 3.9 8.6 121 5.95 × 10−2 3.85 × 10−3 7391

Hex (2) 4.2 5.9 40 4.05 × 10−2 4.13 × 10−3 5031

K2 SO4 5.6 8.5 52 5.84 × 10−2 5.45 × 10−3 7727

KCl (1) 6.0 9.0 50 6.22 × 10−2 5.85 × 10−3 4398

KCl (2) 5.1 7.7 50 5.30 × 10−2 5.00 × 10−3 3742

to maintain the crystals in suspension and as a consequence a higher gas velocity caused bubble coalescence thereby reducing
smaller crystal size distribution will result. the interfacial area.
Table 7 shows the ammonia addition rates used in these tests
and the minimum required to achieve the relevant level of satu-
ration in solution. These rates were calculated from the chemical
Crystal Size
analyses of the barren liquor samples taken during each test. Addi- The crystal size parameters along with the coefficient of varia-
tionally for the hexammoniate tests, ammonia was distributed tion (CV) for each of the tests are shown in Table 8. This table
between both the barren liquor and the crystal product. Hex- indicates that the CV for the initial hexammoniate test (where
ammoniate contains 51% ammonia, but the amount needed to it was assumed that the crystal size was attrition controlled due
produce this crystal was lower than that needed for both K2 SO4 to the high excess ammonia rate) was 60%. However, KCl also
and KCl due to the lower ammonia content in this liquid phase. had a broad size distribution with a CV of 62% commensurate
An excess of 121% was used for the initial hexammoniate test with a crystal having a low degree of attrition (Mersmann, 1995).
but lower excesses were used for the duplicate hexammoniate, Jagadesh et al. (1992) in their work also crystallised KCl using
K2 SO4 , and KCl crystallisation tests. The high gas rate in the initial ammonia and the CV varied between 25.1% and 76.1% while the
hexammoniate test along with the low density of the hexammo- weight mean size varied between 147 and 301 ␮m.
niate crystals contributed to the rounding shown in Figure 3. The second hexammoniate test was the only distribution to
The average mass transfer rate of ammonia achieved in the produce a CV close to the theoretical CV of 50%, which would
tests is also shown in Table 7. These figures were calculated from be obtained from an mixed suspension mixed product removal
the amount of ammonia added to the solutions (and crystals for (MSMPR) crystalliser.
hexammoniate) divided by the time of the test. The crystal density shown in Table 8 also influenced the crystal
All the values in Table 7 are larger than the 110 × 10−6 mol/s, size in these tests. The difference in density between the crystal
which Terasaka et al. (2002) determined in single bubble experi- and the barren liquor was only small for hexammoniate, and as a
ments into H2 O at 298 K at the gas distributor. While it is difficult consequence a small circulation rate in the crystalliser was needed
to compare results from various authors, due to differences in to maintain the crystals in suspension. On the other hand, the
reactor geometries, solution properties, and temperatures, the density difference between crystal and barren liquor for K2 SO4
following points can be made. In their previous work with SO2 was high requiring a higher circulation rate, supplied by a high gas
(Terasaka et al., 1999), they showed that the mass transfer rate rate, to keep these crystals suspended. However, a small ammonia
increased with liquid height. The large liquid height used in excess was used in this test and the settled crystals resulted in a
these GLR tests (0.63 m) would have increased the mass transfer smaller size distribution. These results indicated that the crystal
rate. In addition, the gas rates used were very much smaller than size was dependent on both the gas flow and the crystal density.
the rates used here. The small d50 value of 115 ␮m for the K2 SO4 crystals reflects the
Furthermore, Elperin and Fominykh (1999) in their studies classifying action achieved by the gas flow and the high crystal
showed that the mass transfer rate also increased with the adsor- density.
bate concentration as well as solution density. The higher mass
transfer rates reported here are probably a consequence of the
solution properties and the large liquid height in the GLR. Table 8. Crystal size parameters and coefficient of variation for crystal
As noted earlier, the gas holdup and the mass transfer rate size distributions produced in gas lift crystalliser
increase with the superficial gas velocity and this effect is con-
firmed in the K2 SO4 and KCl tests. In both of these tests, the NH3 Crystal type d16 d50 d84 CV (%) Density (kg/m3 )
content of the barren liquors were approximately 23% although
the salt content of the KCl tests was higher. MgCl2 ·6NH3 (1) 106 192 338 60.0 1350
In all tests the orifice Reynolds number, Reo , was greater than
2000 indicating that the gas flow through the orifice was in the MgCl2 ·6NH3 (2) 148 285 403 45.0 1350
turbulent region. Therefore, the bubble diameter in the crystalliser K2 SO4 75 115 168 40.0 2662a
was not simply related to the orifice diameter and the orifice
Reynolds number (Bhavaraju et al., 1978). KCl (1) 124 238 418 62.0 1988a
In hexammoniate test number 2, a higher mass transfer rate
was achieved at a lower superficial velocity than in test num- KCl (2) 126 196 263 35.0 1988a
a
ber 1. Although slug flow was not evident in test number 1, the Perry (1963).

| 874 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 87, DECEMBER 2009 |
Figure 7. Effect of gas rate on KCl crystal size distribution.
Figure 9. K2 SO4 crystal size plotted against retention time.

Figure 8. Effect of gas rate on hexammoniate crystal size distribution.
This density difference between the K2 SO4 crystals and the bar-
ren liquor was also a problem experienced by Fernandez Lozano
and Wint (1980). Their continuous MSMPR crystalliser needed
a high impeller speed to maintain the crystals in suspension
producing crystals with d50 values between 210 and 232 ␮m.
The variation in the KCl crystal size distribution as a function of
the ammonia flow rate is shown in Figure 7, while the variation
for hexammoniate is shown in Figure 8. Figure 7 provides further
evidence for the gas rate dependence on crystal size for this type of
crystalliser. This figure indicates that the KCl crystal d50 of 238 ␮m
was reduced to 206 ␮m as the excess ammonia was reduced from
9.0 to 7.7 g/min.
However, the hexammoniate distribution became coarser as the
ammonia flow was reduced due to less attrition and secondary
nucleation occurring at this lower circulation rate.
Using Equation (1), the retention times were determined from the
cumulative weight percent of each crystal size distribution using
Microsoft Excel. These were plotted in a similar manner to the data
for the K2 SO4 test at 40◦ C, which is shown in Figure 9. The line
of best fit, constrained to pass through the origin, was drawn to
allow the gradient (growth rate/retention time) to be determined
for each test.
Using this gradient and the retention times, the crystal growth
rates (G) were calculated for each test and these values along
with the crystal slurry density in the crystalliser are shown in
Table 9.
The crystal density and the crystal volume shape factor are
needed to calculate the crystal nucleation rates. The average vol-
ume shape factor for hexammoniate between 355 and 106 ␮m was
determined to be 0.434 using the method of Mullin (1992). The
corresponding values for the K2 SO4 and KCl crystals, by the same
method, were 0.469 and 0.544, respectively.
Garside et al. (1973) determined the shape factor for K2 SO4
crystals of mean size 625 ␮m to be 0.451–0.677, while Budz et al.
(1987) indicated that the shape factor for K2 SO4 crystals is likely
to be size dependent. In their work, the shape factor attained a
maximum of about 2.1 at a crystal size of approximately 100 ␮m,
close to the d50 value of the K2 SO4 crystals produced in this work.
Table 9. Crystal growth rate/retention time, retention time, crystal
slurry density, and crystal growth rates
Test Growth Retention Slurry Growth
rate/retention time (h) density rate (m/s)
time (␮m/h) (kg/m3 )
MgCl2 ·6NH3 49 1.39 185.2 9.8 × 10−9
number1

Crystal Growth Rates MgCl2 6NH3 61 1.46 220.7 11.6 × 10−9

The crystal growth rates and nucleation rates were calculated number2
using the graphical method of Jensen (1986). This method K2 SO4 28 1.02 68.0 7.6 × 10−9
assumes MSMPR operation with:


  KCl number1 68 1.19 75.5 15.9 × 10−9
r3 r2
C = 100 1 − + + r + 1 e−r (1) KCl number2 44 1.26 68.3 9.7 × 10−9
6 2

| VOLUME 87, DECEMBER 2009 | | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 875 |
 Table 10. Growth and nucleation rates and those by previous authors

Crystal Temperature (◦ C) G (m/s) B (number/m3 s)

Current work

Hex (1) MgCl2 6NH3 50 9.8 × 10−9 8.95 × 107

Hex (1) MgCl2 6NH3 50 11.6 × 10−9 5.26 × 107

K2 SO4 K2 SO4 40 7.6 × 10−9 12.6 × 107

KCl (1) KCl 30 15.9 × 10−9 0.864 × 107

KCl (2) KCl 30 9.7 × 10−9 2.73 × 107

Randolph and Rajagopal (1970) K2 SO4 28–35 (3.00–25.1) × 10−9 (4.95–25.4) × 106

Qian et al. (1987) KCl 30 (4.93–13.0) × 10−8 (0.085–1.01) × 106

At crystal sizes >2000 ␮m the shape factor approached 0.5. They
advised caution when comparing previously published data on
the K2 SO4 system due to the possibility that growth rate differ-
ences may be shape factor related.
The nucleation rate (Jensen, 1986), B in number/m3 is given
by:
W ing. Crystallisation of potassium chloride and potassium sulfate
B= (2)
6kv c G3 r 4
In the present work the calculated growth and nucleation rates,
determined from Equation (2), are shown in Table 10.
Variability is observed between the growth and nucleation
rate calculated by various authors. Reasons for this variability,
apart from shape factor, are due to temperature, viscosity, super-
saturation levels, crystalliser geometries and rpm, crystalliser
solids content, and the impurity level in solution to name but
a few. Nevertheless, some values determined by previous workers
for the KCl and K2 SO4 systems are shown in Table 10.
The growth rates and nucleation rates for the KCl crystals were
slightly different from those of Qian et al. (1987), being slightly
lower and slightly higher, respectively. The higher nucleation
rates are perhaps due to the higher crystal suspension densities in
the current tests producing more secondary nuclei. The solids con-
centration, in the K2 SO4 work by Randolph and Rajagopal (1970),
between 7 and 28 g/L was also less than half of the concentration
in the current work.
transfer rates achieved were a lot higher than those of Terasaka et
al. (2002), who obtained their data with single bubbles into H2 O
at 298 K.
While GLRs are low shear type reactors, rounded crystals of
hexammoniate were formed due to the hydrodynamics of the crys-
talliser and the attrition prone nature of these crystals. The vast
excess of ammonia used (121%) contributed to the crystal round-
produced cubic crystals, which showed no rounding.
In crystallisation, all particles need to be suspended in the
mother liquor to provide the maximum possible surface area for
homogenous conditions of mass transfer from the liquid to the
solid phase. The difference in density between the hexammoni-
ate and its barren liquor was small, and a small circulation rate
was needed to maintain the crystals in suspension. The crystal d50
in this case was high at 285 ␮m but was only 115 ␮m for K2 SO4
where there was a large density difference and some crystals set-
tled. Therefore, when using a gas lift crystalliser, the gas rate needs
to be optimised for each crystallising system to achieve sufficient
gas mass transfer as well as providing sufficient crystal slurry
agitation.
Crystal growth and nucleation rates were determined for the
three types of crystals produced by salting-out with NH3 . While
the growth rates for both potassium chloride and potassium sul-
fate were similar to previously determined values, the nucleation
rates for these crystals were higher than previously reported
values.

CONCLUSION
A laboratory-scale GLR was used to crystallise magnesium chlo- NOMENCLATURE
ride hexammoniate, potassium chloride, and potassium sulfate AD cross-sectional area of downcomer (m2 )
by salting-out with ammonia gas. In GLRs, both the agitation and AR cross-sectional area of riser (m2 )
the mass transfer functions are supplied by the incoming gas and B nucleation rate (number/m3 s)
therefore excess ammonia was needed above that used to salt-out C cumulative weight (%)
the crystals. This excess varied between 50% and 121% with the d16 particle diameter where 16% are sized smaller (␮m)
latter amount used in one hexammoniate test. d50 particle diameter where 50% are sized smaller (␮m)
Ammonia mass transfer rates varied between 3.8 × 10−3 and d84 particle diameter where 84% are sized smaller (␮m)
5.8 × 10−3 mol/s and for most tests these increased as the gas G crystal growth rate (m/s)
superficial velocity increased. However, a lower ammonia mass kv volumetric shape factor
transfer rate was obtained in the hexammoniate test, which used r number of retention times
121% excess gas. This lower rate may have been due to greater Reo orifice Reynolds number
bubble coalescence at this high superficial velocity. The mass W crystal slurry density (kg/m3 )

| 876 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 87, DECEMBER 2009 |
Greek Symbols
εGR gas holdup
c crystal density (kg/m3 )
ACKNOWLEDGEMENTS
The author gratefully acknowledges Ms. Jill Rounds and Ms. Jean
Deacon from CSIRO Minerals Library for obtaining many refer-
ences. Many thanks to Ms. Kyra Van Den Bos of The Chemical
Institute of Canada for her editorial assistance during the prepa-
ration of this manuscript. Thanks are also extended to the CSIRO
Minerals Analytical Services and to Ms. Sophia Saunders and Mr.
Roman Ruzbacky for their contributions to this work.
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Manuscript received February 4, 2009; revised manuscript

received March 25, 2009; accepted for publication June 4, 2009.

| 878 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 87, DECEMBER 2009 |