Chemical Engineering Journal 419 (2021) 129428

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Chemical Engineering Journal

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The extraction of hexamethylenediamine from aqueous solution by pH

control and salt addition
The extraction of HMD from aqueous solution by NaOH and salt
Michael J. Sargent a ,∗, Nigel K.H. Slater a , John S. Dennis a , Gary J. Smith b , Paul S. Pearlman b
a
Department of Chemical Engineering and Biotechnology, University of Cambridge, West Cambridge Site, Cambridge, UK
b
INVISTA Textiles (U.K.) Limited Redcar, UK

ARTICLE INFO ABSTRACT

Keywords: This paper details an investigation into the separation of Hexamethylenediamine (HMD) from dilute aqueous
Phase separation solutions by exploiting phase separation. HMD is a monomer used in the production of Nylon-6,6 and as
Amine such this separation is potentially useful in extracting purifying HMD produced from biological sources or
Salt
reclaimed from waste made by the production of nylon. An investigation was undertaken into the effect of
Hexamethylenediamine
using sodium hydroxide (NaOH) to promote the phase separation, and a model was derived to predict this
Nylon
behaviour. Furthermore, the effect of various salts on this phase separation was investigated, and it was found
that sodium sulphate and sodium carbonate promote the phase separation, but are unable to cause phase
separation without the presence of sodium hydroxide.

1. Introduction
Hexamethylenediamine, hereafter referred to as HMD, is an un-
branched 6 carbon chain, terminated at each end by an amine group.
This makes it an important monomer for the production of nylons,
particularly nylon-6,6, in which it is reacted with adipic acid. Due to
the presence of the amine groups, it is highly soluble in water.
Historically HMD has been produced from petrochemical sources,
including acrylonitrile, butadiene, and cyclohexane [1]. As an alterna-
tive to this, there have been efforts to produce HMD from biological
processes or feedstocks [2–6]. A drawback of these biological methods
of HMD production is that the concentration is low [7], necessitating
the separation and purification of dilute HMD solutions. However, some
progress has been made towards the biological production of higher
concentrations of similar molecules [8].
Established purification methods for HMD are commonly based
on thermal processes such as distillation or crystallisation, in which
the secondary component may be water [9], ammonia [10], or a
mixture of the two [11,12]. More recent advances in HMD purifica-
tion have tended to focus on removing specific impurities which are
usually byproducts of HMD production, such as imines [13,14] or
aminocapronitrile [15,16]. Whilst these methods are well tailored to
the problems of HMD separation and purification from conventional
feedstocks, they are not necessarily applicable to HMD processing from
biological feedstocks.
To this end, an investigation was made into methods for extracting
HMD from aqueous solutions at concentrations below 50 g L−1 . Initially
chromatographic methods of separation were used, however a chance
discovery showed that HMD can spontaneously form a secondary phase
under some conditions, when the pH was raised high enough. Since this
secondary phase contained HMD at a concentration above 500 g L−1 , it
was decided that this was a valid alternative method for the extraction
of HMD in its own right.
In this paper, the phase separation behaviour of HMD in aqueous
solutions is investigated as a new and separate principle on which to
achieve purification. Firstly the effect of only adding sodium hydroxide,
hereafter referred to as NaOH, is quantified, and a model for the phase
compositions is developed to allow for the design of separation process
equipment. Then, the effect of various salts on the phase separation
was looked into. This was chosen as the NaOH addition was observed to
have similarities with protein extraction by salting-out [17]. Salting-out
has also been used to assist liquid–liquid extraction of amines within
the food [18,19] and dye [20,21] industries.
In this work, contaminants to the HMD were not included, as would
be present in any fermentation broth. This was chosen for two reasons.
The first is simplification, to reduce the number of species present in

∗ Corresponding author.
E-mail address: mjs44@cam.ac.uk (M.J. Sargent).
URL: https://www.ceb.cam.ac.uk/directory/michael-sargent (M.J. Sargent).

https://doi.org/10.1016/j.cej.2021.129428
Received 18 August 2020; Received in revised form 11 March 2021; Accepted 15 March 2021
Available online 25 March 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
M.J. Sargent et al.
Fig. 1. Speciation of HMD. Fraction of HMD in each charge valence state, HMD2+,
HMD+, or uncharged, as a function of pH.
Fig. 2. Two phase system. Three samples showing phase separation in the presence of both
HMD and NaOH, each 1 mL. A - 50 g L−1 of HMD. B - 50 g L−1 of HMD and 250 g L−1
of NaOH. C - 250 g L−1 of NaOH. Arrows show menisci positions.
the system. The second is that this research is also valid for the recovery
of HMD from waste streams in the production of Nylon-6,6, in which
HMD is used in excess to the other reagents and so there will be some
HMD to recover [22].
2. Materials and methods
The first indication of phase separation involving HMD came about
while preparing samples of HMD at high pH by the addition of large
quantities of NaOH. Fig. 1 shows the relative mole fractions of HMD in
each valence state as a function of pH.
At sufficiently high pH all of the HMD is in the non-valent state.
Thus, the HMD behaviour is that of an uncharged hydrocarbon chain,
which is hydrophobic.
Fig. 2 shows an example of this separation. Sample A contains 50
g L−1 of HMD in water. Sample C contains 250 g L−1 of NaOH in water.
Sample B contains both 50 g L−1 of HMD and 250 g L−1 of NaOH.
It can be seen that the inclusion of both HMD and NaOH has caused
spontaneous separation into two distinct phases: a small quantity of an
HMD-rich lighter phase and a larger quantity of a denser phase. The
lighter phase is organic, containing a high concentration of HMD in its
non-valent state with some residual water. The denser phase is aqueous,
containing a high concentration of NaOH in water, with some residual
HMD.
2.1. Solution preparation
Solutions containing carefully controlled concentrations of HMD
and NaOH were prepared by first mixing stock solutions. Different
2
Chemical Engineering Journal 419 (2021) 129428
quantities of these stock solutions were then pipetted together to make
different combinations of total concentrations, to observe which would
undergo phase separation. All chemicals used for the production of
these solutions was supplied by Sigma Aldrich, with the exception of
the deionised water.
The HMD stock solution was made using 101 ± 1 g of 99%+ purity
HMD, dissolved into deionised water in a 1000 ± 1 mL volumetric flask.
Therefore the concentration of the stock solution was 100 ± 1.4 g L−1 of
HMD.
The NaOH stock solution was made using 102 ± 1 g of 98%+ purity
NaOH, dissolved into deionised water in a 200 ± 1 mL volumetric flask.
Therefore the concentration of the stock solution was 500 ± 12 g L−1 of
NaOH.
The third stock solution was simply deionised water. The combina-
tion of these three stock solutions could make a range of different total
concentrations.
2.2. Concentration measurement
The concentration of HMD in solutions was measured using an
Agilent 6850 series gas chromatograph, fitted with a CP-Sil 8 CB for
Amines column. The internal standard used for concentration calibra-
tion made from 10 mL of hexylamine and 40 g of NaOH, dissolved into
1 L of an equal volume mixture of water and methanol. The hexylamine
provided the standard peak, and the NaOH served to raise the pH of the
samples and ensure that the HMD present was in its non-valent state, as
the valent states of HMD have inconsistent evaporation behaviour. The
mixture of water and methanol as solvents allowed this single internal
standard to be used for samples of either an aqueous or organic nature.
A multipoint calibration curve was made for HMD concentrations
of up to 100 g L−1 , as samples within this range of concentrations
was easily produced from the stock solutions described in Section 2.1.
The organic phases resulting from the phase separation have higher
concentrations than 100 g L−1 , and so these were diluted 1 part in 10
with an equal volume mixture of water and methanol. This dilution
brought the HMD concentration into the measurable range, however
in converting from measured concentration back to original sample
concentration, there is an extra contribution to the uncertainty in the
concentration from both the dilution ratio, and the uncertainty in that
ratio.
The concentration of NaOH in solutions was measured using a
Mettler Toledo PerfectION™ sodium-selective ion probe. Whilst this
technically measures the sodium ion concentration, samples produced
from only deionised water, HMD, and NaOH contain no other anions
in significant quantities. Thus, wherever sodium ions are observed, it
is assumed that they are part of dissolved NaOH.
The ion probe had a maximum measurable ion concentration of 1
mol L−1 , which is equivalent to 40 g L−1 of NaOH. The concentrations
of NaOH in all aqueous samples was higher than this limit, and so
these samples were diluted 1 part in 10 with deionised water to be
able to measure the concentration of NaOH. Deionised water was
used in place of the mixture of water and methanol which was used
for dilutions required in the HMD measurement, as only the aqueous
samples required dilution, and it was desired to avoid altering the ionic
strength of the solvent by the addition of the nonionic methanol. This
dilution resulted in the same increase in concentration uncertainty that
was mentioned for concentrated HMD samples which required dilution,
and some samples were so highly concentrated in NaOH that a dilution
of 1 part in 20 was required.
3. Experimental results
The stock solutions described in Section 2.1 allowed for samples to
be made at a wide range of concentrations for both HMD and NaOH.
66 samples were prepared to map out the concentration-space, and to
find the region in which spontaneous phase separation occurs. The total
M.J. Sargent et al. Chemical Engineering Journal 419 (2021) 129428

Fig. 3. Phase separation region. Preliminary work in assessing the phase separating region Fig. 4. Tie line error analysis. Tie lines, linking aqueous and organic phases in equilibrium
of the concentration-space of the water/HMD/NaOH system. Error bars are given by the size with each other, through the total concentration which underwent phase separation. Raw data
of the symbols. is shown alongside the correction to account for errors in concentration measurements.

volume of the stock solutions used to prepare these samples was 10 mL,
and there was negligible volume change on mixing. This data is shown
in Fig. 3.
Each symbol in Fig. 3 represents a sample made to a different
choice of concentrations for HMD and NaOH. Error bars for these
concentrations are given by the sizes of the symbols. 22 of the samples
exhibited phase separation, forming a small quantity of an organic
phase in addition to the much larger volume of aqueous phase. This
data so far gives a rough indication of the conditions required for phase
separation to occur.

3.1. Tie line correction

To continue to investigate the equilibrium of the phase separa-

tion, each of the 22 samples from Fig. 3 which formed an organic
phase were separated, and the volume, HMD concentration, and NaOH
concentration of both the aqueous phase and the organic phase were
recorded. Due to uncertainties in the concentration measurements, the
mass of each species does not always balance between the total, and
the subsequent separated phases.
𝑥𝑡𝑜𝑡 = (1 − 𝛷)𝑥𝑎𝑞 + 𝛷𝑥𝑜𝑟𝑔
𝑦𝑡𝑜𝑡 = (1 − 𝛷)𝑦𝑎𝑞 + 𝛷𝑦𝑜𝑟𝑔
We expect that the concentrations of HMD, 𝑥, and NaOH, 𝑦, to
obey the mass balance given in Eq. (1). The subscripts refer to the
phase of each concentration, 𝑡𝑜𝑡 refers to the total made from the stock
solutions, and 𝑎𝑞 and 𝑜𝑟𝑔 refer to the separated aqueous and organic
phases respectively. 𝛷 is the fraction of the total volume of the two
phases which is occupied by the organic phase, as given by Eq. (2).
𝛷 = 𝑉𝑜𝑟𝑔 ∕𝑉𝑡𝑜𝑡
Each of the seven variables used in Eq. (1) has been measured to
give value and its uncertainty. The mass balances given in Eq. (1) can
be used to generate updated values for the variables. An example of
this is shown graphically in Fig. 4.
Fig. 4 shows two sets of data; that of the raw data for the concen-
trations, and the corrected values based on the mass balance. For the
concentrations to satisfy the mass balance, the three points for the total,
aqueous phase, and organic phase must be co-linear. Additionally, the
distance from the aqueous point to the total point, as a fraction of the
distance from the aqueous point to the organic point, must be equal to
the volume fraction 𝛷.
The corrected concentrations are determined by minimising the
residual sum of squares for the change in each of the seven variables,
Fig. 5. Experimental tie lines. All experimental tie lines linking aqueous and organic phases
in equilibrium with each other, after the application of error correction.
relative to the original uncertainty in that variable. This is shown
(1)
in Eq. (3). The result of this method of error correction is that the values
with the highest degree of uncertainty receive the most change.
( )2
corrected value − raw value
𝑅𝑆𝑆 = 𝛴 (3)
raw uncertainty
Fig. 4 reflects this, as the highest uncertainties lie with the NaOH
concentration in the aqueous phase, and the HMD concentration in
(2) the organic phase. Both of these uncertainties are high as a result of
the dilution process required to bring these concentrations into the
measurable range of their respective instruments. This method of error
correction was applied to the data from all 22 samples which were
observed to undergo phase separation, and the resulting data is shown
in Fig. 5.
Fig. 5 shows these 22 samples which underwent phase separation in
the form of tie lines. These are lines which link points in concentration-
space which are in equilibrium with each other [23]. From these
tie lines, we can observe trends in the equilibrium behaviour which
is governing the phase separation. It can be seen that for samples
containing lower total concentrations of either species have shorter tie
lines, which corresponds to aqueous and organic phases which are more
similar in composition.

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M.J. Sargent et al. Chemical Engineering Journal 419 (2021) 129428

3.2. Equilibrium modelling

The experimental tie lines shown in Fig. 5 represent a thermody-

namic equilibrium between two phases. To make use of this thermody-
namic information as a tool for phase separation, a model was derived
which can accurately predict what concentrations are required for
phase separation to occur, and what the compositions of the resulting
separated phases would be.
The first step in devising the model was to quantify the tie line loca-
tions and gradients. The experimental tie lines are not all parallel, nor
do they all intercept at a common point. Instead, a gradual steepening
of the gradient was observed for tie lines which were further away from
the origin of Fig. 5.
One way in which this behaviour can be captured is by drawing a
curve on these axes of 𝑥 and 𝑦, and approximating each tie line by a
tangent to this curve at a different point along its length. For this system
a quadratic curve was used, given by Eq. (4).

𝑦 = 𝑎0 + 𝑎1 𝑥 + 𝑎2 𝑥2 (4) Fig. 6. Tie line gradient modelling. Experimental tie lines, compared to a model for
predicting the gradients of the tie lines.
At any point along the length of this curve, (𝑥𝑇 , 𝑦𝑇 ), a tangent line
to the curve can be drawn. This tangent line will have a gradient, 𝑚,
that is the same as the local gradient of the quadratic, given by Eq. (6).
( )
𝑑𝑦
𝑚= = 𝑎1 + 2𝑎2 𝑥𝑇 (5)
𝑑𝑥 𝑥=𝑥
𝑇

From the gradient and the intercept point with the quadratic, the
equation of the line can be determined for each possible tangent point.

𝑦 − (𝑎0 + 𝑎1 𝑥𝑇 + 𝑎2 𝑥2𝑇 ) = 𝑚(𝑥 − 𝑥𝑇 ) (6)

By using Eqs. (4) to (6), we can arrive at an expression for the

tangent 𝑥 value, Eq. (7), or the gradient, Eq. (8), from only knowing
the total concentrations of HMD, 𝑥𝑡𝑜 , and NaOH, 𝑦𝑡𝑜𝑡 . This allows
us to identify which individual tie line any possible combination of
concentrations will fall on.
√
𝑥𝑇 = 𝑥𝑡𝑜𝑡 + 𝑥2𝑡𝑜𝑡 + (𝑎1 𝑥𝑡𝑜𝑡 + 𝑎0 − 𝑦𝑡𝑜𝑡 )∕𝑎2 (7)
√
𝑚 = 2𝑎2 𝑥𝑡𝑜𝑡 + 2𝑎2 𝑥2𝑡𝑜𝑡 + (𝑎1 𝑥𝑡𝑜𝑡 + 𝑎0 − 𝑦𝑡𝑜𝑡 )∕𝑎2 − 𝑎1 (8)

The parameters in Eq. (4) were manipulated until these model

predicted tie lines matched up with both the locations and gradients
of the experimentally determined tie lines. The resulting fit uses the Fig. 7. Aqueous phase concentration modelling. Model fitting for the concentrations of
parameters given in Eq. (9), and the comparison of the experimental each species in the aqueous phase, as a function of the gradient of the model tie line which
and model tie lines is shown in Fig. 6. the total concentration lies on.

𝑎0 = −1.6687 × 10−4 [g L−1 ]

𝑎1 = −0.0912 [−] (9)
𝑎2 = 84.5836 [L g−1 ]
The model tie lines form a good match to the experimental tie
lines, however at high total concentrations there is a difference in
gradient. The experimental tie line labelled A is for the highest total
concentration of HMD and NaOH, which also has the highest degree
of uncertainty in it concentration measurements, due to the necessary
dilutions discussed in Section 2.2.
Now that we have a model for predicting the tie line locations
and gradients, the next step is to determine where the ends of the
lines lie, which correspond to the exact concentrations present in each
phase. As we have Eq. (8) to determine the tie line gradient, 𝑚, for
any possible combination of total concentrations, we will model these
endpoint concentrations by their dependence on 𝑚. As our tie lines are
sloping downward, values of 𝑚 are negative, and the lower the value
of 𝑚 is, the further from the origin it lies.
First, consider the aqueous phase, which will be the upper left end
of the tie lines as they appear in Fig. 6. If we first perform a fitting for
the concentration of one of the components as a function of 𝑚, then this
automatically assigns the concentration of the other component. This
is because a given value of 𝑚 corresponds to a single tie line, which
already links the concentrations of our two components by being a line
in concentration-space. Therefore, one function must fit to two sets of
data; both the HMD concentrations and the NaOH concentration. The
concentrations of both HMD and NaOH in the aqueous phase are shown
in Fig. 7.
The fitting lines shown in Fig. 7 were arrived at by the following
method. First, the dependence of the aqueous HMD concentration,
𝑥𝑎𝑞 , on the tie line gradient, 𝑚, was observed to have an exponential
relationship, as given by Eq. (10). This dependence was used as it
predicts a finite, non-negative concentration, even for arbitrarily low
values of the tie line gradient, which correspond to tie lines with very
high total concentrations of HMD and NaOH.
𝑥𝑎𝑞 = 𝑏0 + 𝑏1 exp(𝑏2 𝑚) (10)
Through use of the generic tie line, Eq. (6), the aqueous NaOH
concentration, 𝑦𝑎𝑞 , is also set by Eq. (11). Thus, a single set of param-
eters used to fit both of these curves to the experimental data. The

4
M.J. Sargent et al. Chemical Engineering Journal 419 (2021) 129428

Fig. 9. Tie line model. Model for the phase separating region of the HMD–NaOH system,
Fig. 8. Organic phase concentration modelling. Model fitting for the concentrations in the allowing prediction of compositions of separated phases and fraction of each phase. Tie lines
organic phase, as a function of the gradient of the model tie line which the total concentration are shown in decrements of 0.02 gradient below the plait point at 𝑚 = −0.2857. Volume
lies on. fraction lines are shown in increments of 10%.

parameters which were used in Fig. 7 are shown in Eq. (12). If the volume fraction lies outside the range (0, 1), it implies that the
( ) ( ) ( )
𝑎2 𝑎1 original composition will not undergo phase separation, as it cannot
1
𝑦𝑎𝑞 = 𝑎0 − 1 + 𝑚− 𝑚2 + 𝑚𝑏0 + 𝑚𝑏1 exp(𝑏2 𝑚) (11) balance mass of two phases in equilibrium. Another case to consider
4𝑎2 2𝑎2 4𝑎2
is that the tie line falls below the Plait point, which is the point at
𝑏0 = 3.050 [g L−1 ] which the tie line separating the two phases has no length, and so the
𝑏1 = 3027 [g L−1 ] (12) two phases would have the same composition. The plait point can be
𝑏2 = 41.86 [−] located by finding the value of 𝑚 at which the organic and aqueous
Whilst the concentrations of the two components within each phase concentration are predicted to have the same values, and for this fitting
are linked to one another, the fitting for the organic phase is entirely corresponds to 𝑚 = −0.2857. Therefore, if the value of 𝑚 calculated in
separate from that of the aqueous phase. However, the aqueous con- step 1 above is above this value, phase separation cannot occur.
centrations of HMD and NaOH are similarly linked to one another in This model is illustrated in Fig. 9. The diagonal lines are the tie
the organic phase. The concentrations of both HMD and NaOH in the lines, truncated to the concentrations predicted for the organic and
organic phase are shown in Fig. 8. aqueous phases. The curved lines denote the volume fraction of organic
The fitting lines shown in Fig. 8 were arrived at by a similar phase from 0%, which corresponds to only the aqueous phase, in
method to that used for Fig. 7, however the order of the components increments of 10% up to 100%, which corresponds to only the organic
was reversed. For the organic phase, the first component to have phase.
a fitting equation assigned to it was the NaOH concentration, 𝑦𝑜𝑟𝑔 ,
where the aqueous phase first fitted to the HMD concentration. This 4. Salt addition
dependence was again observed to follow an exponential relationship,
given by Eq. (13), for the same reasons as before. With the phase separation behaviour of the three component system
fully quantified, the next step is to investigate other compounds that
𝑦𝑜𝑟𝑔 = 𝑐0 + 𝑐1 exp(𝑐2 𝑚) (13)
could be added to promote the phase separation. The spontaneous
Once more, the tie line was used to convert this NaOH concentration generation of a second phase rich in HMD by the addition of NaOH was
into the equivalent HMD concentration, given by Eq. (14). Both of these identified as being similar to the separation of proteins from aqueous
equations were used to fit the parameters in Eq. (13), which are shown solutions using salts. The solubility of proteins in aqueous solutions can
in (15). be increased or decreased by the presence of salts, termed salting-in or
( ) ( ) ( ) salting-out respectively [17,24].
𝑎21 1 𝑎1 1 𝑐 𝑐
𝑥𝑜𝑟𝑔 = − 𝑎0 − − + 𝑚 + 0 + 1 exp(𝑐2 𝑚) (14) The first salt to be tested was sodium sulphate, Na2 SO4 . This was
4𝑎2 𝑚 2𝑎2 4𝑎2 𝑚 𝑚
chosen because it is the result of neutralising sodium hydroxide with
𝑐0 = 2.742 × 10−7 [g L−1 ] sulphuric acid, both of which are used during the nylon-6,6 production
𝑐1 = 3601 [g L−1 ] (15) process [22,25]. From this sodium sulphate a range of other salts were
𝑐2 = 13.12 [−] tested, by changing either the anion or cation.
The model is now complete, in that it can completely predict all
the properties of a system which undergoes phase separation. The 4.1. Solution preparation
procedure for using the model for a given theoretical mixture of HMD
and NaOH is as follows: Stock solutions for these salt addition tests were produced by the
same formulations as given in Section 2.1., with a few modifications.
1. Using the concentrations of HMD and NaOH, calculate the gra- Firstly, the HMD stock solutions were made up to 500 g L−1 , to allow
dient of the tie line which that mixture lies on (Eq. (8)). for samples to be made in closer concentrations to the organic phases
2. Using the tie line gradient, calculate the concentrations of each produced by the phase separation. Secondly, the salts were added to
component in each phase (Eqs. (10), (11), (13), and (14)). all three stock solutions in the same concentration. The result of this is
3. Using the compositions of each phase, calculate the volume that any combination of these salted stock solutions will maintain the
fraction of the total which is occupied by the organic phase (Eq. same salt concentration, so that only the effect of the HMD and NaOH
(1)). concentrations can be observed.

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M.J. Sargent et al. Chemical Engineering Journal 419 (2021) 129428

Table 1
Salts tested for effect on phase separation behaviour.
Salt name Cation Anion Concentration
[g L−1 ]
Sodium sulphate Na+ SO2−
4
100
Sodium chloride Na+ Cl− 82.3
Sodium iodide Na+ I− 211
Sodium nitrate Na+ NO−3 120
Sodium carbonate Na+ CO2−
3
74.6
Potassium sulphate K+ SO2−
4
123
Ammonium sulphate NH+4 2−
SO4 93.0
Zinc sulphate Zn2+ SO2−
4
114

The concentration of Na2 SO4 used in the corresponding three stock

solutions was 100 ± 2 g L−1 . Therefore the compositions of these stock
solutions were as follows:

• An HMD/Na2 SO4 stock solution, containing 500±14 g L−1 of HMD Fig. 10. Sodium series. Effect of different sodium salts on the location of the phase
and 100 ± 2 g L−1 of Na2 SO4 . boundary for the HMD–NaOH system. Salts may increase or decrease the solubility of HMD,
• An NaOH/Na2 SO4 stock solution, containing 500 ± 12 g L−1 of which raises or lowers the required amount of NaOH to cause phase separation. All salts
NaOH and 100 ± 2 g L−1 of Na2 SO4 . are present at the same sodium ion concentration as 100 g L−1 Na2 SO4 .

• A water/Na2 SO4 stock solution, containing only 100 ± 2 g L−1 of

Na2 SO4 .

This process was repeated for all of the different salts, which are
shown in Table 1. The mass concentrations of each salt were chosen
to ensure that each salt has the same sodium ion or sulphate ion
concentration as sodium sulphate, whichever was appropriate.

4.2. Phase boundary detection

Instead of repeating the same tie line analysis and modelling that
was used for the three component system, a simplified analysis of the
phase separation behaviour was used to investigate the effect of the
addition of these salts.
In the first stage, solutions at different concentrations of HMD
were titrated with the NaOH stock solution until the presence of a
secondary phase was observed. Then in the second stage, solutions at
different concentrations of NaOH were titrated with the HMD stock
solution, until the secondary phase was again observed. By recording
Fig. 11. Sulphate series. Effect of different sulphate salts on the location of the phase
the volumes of each solution in each titration, the location of the phase boundary for the HMD–NaOH system. Salts may increase or decrease the solubility of HMD,
boundary in concentration-space can be determined without having to which raises or lowers the required amount of NaOH to cause phase separation. All salts
perform the full tie line analysis. are present at the same sulphate ion concentration as 100 g L−1 Na2 SO4 .

4.3. Sodium salts

The phase boundaries determined by titration for all of the sodium
salts are shown in Fig. 10. These are compared to the phase boundary
in the case with no added salt, which is that of the three component
system.
It can be seen that each salt shows a phase boundary as an un-
certainty region, between concentrations which were confirmed to be
single phase, and those confirmed to be two phase. The effect of each
salt on promoting or hindering the phase separation is shown by the
way that the location of the phase boundary region has shifted, relative
to the case with no salt.
Sodium iodide has shifted the phase boundary up relative to the
case with no salt. This means that some concentrations which undergo
phase separation in the three component system will not undergo
phase separation when sodium iodide is present at this concentration.
Therefore, the sodium iodide has increased the miscibility of HMD and
NaOH, and hindered the phase separation.
The addition of sodium chloride and sodium nitrate have had very
little effect on the location of the phase boundary. There is a slight shift
up for the nitrate salt, and down for the chloride salt, but the majority
of the uncertainty regions for the phase boundary overlap between
these two salts and the case with no salt.
The addition of sodium carbonate and sodium sulphate both shifted
the phase boundary down, relative to the case with no salt. This
indicates that these salts promote the phase separation, meaning that a
lower concentration of NaOH is required to cause phase separation to
occur, for a constant HMD concentration. These show a phase boundary
in a similar location to that given for sodium hydroxide.
The behaviour for NaOH is arrived at by treating some of the NaOH
already present in the system as if it was a salt. Therefore the location of
the phase boundary is that of the boundary for the no salt case, shifted
down by 56.3 g L−1 . This is the mass concentration of NaOH which
results in the same sodium ion concentration as any of the other salts.
4.4. Sulphate salts
The phase boundaries determined by titration for all of the sulphate
salts are shown in Fig. 11. Again, these are compared to the phase
boundary in the case with no added salt.
The addition of zinc sulphate and ammonium sulphate salts has
a different effect to the previous salts. Instead of simply shifting the

6
M.J. Sargent et al.
Fig. 12. Comparison of all salts. Effect of each salt on the area of the single phase region
of the concentration-space for the HMD–NaOH system. All salts are present at the same
sodium ion or sulphate ion concentration as 100 g L−1 Na2 SO4 . NaOH is shows for basic
comparison to the neutral salts.
phase boundary, the gradient of the boundary increases. This means
that these salts hinder phase separation for low HMD concentrations,
relative to the case with no salt, but promote phase separation at
high HMD concentrations. In particular, ammonium sulphate appears
to once more hinder phase separation for HMD concentrations above
400 g L−1 , although this may be attributed to the large uncertainties in
these values.
The other salts, potassium sulphate and sodium sulphate, both
promote phase separation by lowering the phase boundary. Potassium
has less of an effect than sodium, at the same molar concentrations.
4.5. Salt comparison
It should be noted that of all the salts tested in this section, none of
them were capable of causing HMD to phase separate in the absence
of any NaOH. Increasing the concentration of each salt reached their
respective solubility limits before they raised the ionic strength of the
mixture high enough to cause spontaneous phase separation. This is
likely due to the fact that the natural pH of HMD solutions is around
11, under which conditions the speciation of the HMD results in only
a small fraction in the non-valent state.
To compare the effectiveness of the different salts, we must look at
the area of the single phase region. By calculating the area under the
phase boundaries for each salt in Figs. 10 and 11, we get a quantitative
measure of how each salt promotes or hinders the phase separation.
These areas are divided by the area under the phase boundary in the
case of no salt, to obtain relative measures of the phase separation
behaviour. This data is shown in Fig. 12.
As phase separation is the desired behaviour, the lower values of
relative area are desired as they reduce miscibility and promote the
formation of the organic phase. Therefore it can be seen straight away
that sodium iodide, sodium nitrate, and zinc sulphate salts should be
avoided as they hinder phase separation.
All of the divalent anions promote phase separation. This may be
due to the fact that the ionic strength of a mixture is dependent on
the square of the charge of the ions, and it is the ionic nature of the
aqueous phase which is at odds with the organic, nonvalent HMD. The
best cation for promoting phase separation is sodium.
7
Chemical Engineering Journal 419 (2021) 129428
5. Conclusions
It has been shown that sufficient quantities of sodium hydroxide
(NaOH) can cause aqueous solutions of hexamethylenediamine (HMD)
to undergo phase separation, splitting the diamine into its own organic
phase.
This work has investigated the mechanism by which these sepa-
rate phases become thermodynamically favourable. Section 2 showed
that the pH of a solution of HMD will alter the charge on each
HMD molecule. At the higher pH values caused by the addition of
NaOH, the HMD becomes an uncharged hydrocarbon, and therefore
has unfavourable mixing with the polar water molecules. In addition,
Section 4 showed how increasing the ionic strength of the solution
without altering the pH can also promote phase separation. The quan-
tity of NaOH required to use this principle on a useful scale may be
prohibitively high, depending on economic factors, but can be reduced
by recycling of the produced aqueous phase.
This work has also derived a model by which the compositions
of the separated phases can be predicted, given in Section 3.2. This
allows for the practical use of this phase separation behaviour for
the extraction of HMD from aqueous solutions. Two such examples of
where this may be useful were given in Section 1, for the extraction
of HMD produced by fermentation from the broth, and the recovery of
HMD from waste streams generated during the processing of nylon-6,6,
however experimental testing of such systems has been prevented by
current events.
Nomenclature
HMD Hexamethylenediamine
NaOH Sodium hydroxide
𝑥 Concentration of HMD (generic)
𝑥𝑎𝑞 ... in the aqueous phase
𝑥𝑜𝑟𝑔 ... in the organic phase
𝑥𝑡𝑜𝑡 ... in total across both phases
𝑦 Concentration of NaOH (generic)
𝑦𝑎𝑞 ... in the aqueous phase
𝑦𝑜𝑟𝑔 ... in the organic phase
𝑦𝑡𝑜𝑡 ... in total across both phases
𝑎𝑛 Parameter n from the tie line tangent quadratic fit
𝑏𝑛 Parameter n from the aqueous HMD concentration fit
𝑐𝑛 Parameter n from the organic NaOH concentration fit
𝑚 Tie line gradient
𝛷 Volume fraction of the organic phase
𝑉𝑜𝑟𝑔 Volume of the organic phase
𝑉𝑡𝑜𝑡 Total volume
Declaration of competing interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
M.J. Sargent et al.
Acknowledgement
The authors would like to thank INVISTA Textiles (U.K.) Limited
funding for this work.
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