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14 The separation of hexamethylenediamine from aqueous solution by solvent extraction with butanol - ScienceDirect

Separation and Purification Technology

Volume 288, 1 May 2022, 120655

The separation of hexamethylenediamine from

aqueous solution by solvent extraction with
butanol
Michael J. Sargent a, Nigel K.H. Slater a, J.S. Dennis a , Gary J. Smith b, Paul S. Pearlman b

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https://doi.org/10.1016/j.seppur.2022.120655
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Highlights

• Butanol is suitable for extracting hexamethylenediamine from dilute aqueous

solution.

• Addition of sodium hydroxide resulted in improved separation.

• Model derived to predict partitioning of HMD between aqueous and organic

phases.

• Extraction of HMD produced biologically or reclaimed from nylon recycling.

Abstract

This paper details an investigation into the separation of hexamethylenediamine (HMD) from
dilute aqueous solutions by solvent extraction. This separation is potentially useful in (i)
reclaiming HMD from waste generated in the production of nylon, (ii) for extracting HMD
produced by fermentation, or (iii) reclaiming it from waste emanating from the
depolymerization of nylon during recycling. Butanol was identified as a suitable solvent for the

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28/02/24 15.14 The separation of hexamethylenediamine from aqueous solution by solvent extraction with butanol - ScienceDirect

preferential dissolution of HMD from an aqueous solution, and it was found that the addition of
sodium hydroxide resulted in improved separation. It was deduced that HMD has a bridging
effect on the partial miscibility of water and butanol, and approximately 10 wt% of HMD was
sufficient to allow for complete miscibility and the avoidance of phase separation. However, the
addition of NaOH to the system reversed this bridging effect and reduced the solubility of
butanol in the aqueous phase whilst also increasing the partitioning of HMD between the
organic and aqueous phase.

A model for an equilibrium mixer-settler unit was developed with three important findings
emerging. Firstly, the amount of water which could be dissolved in the organic phase was
found to increase with the amount of HMD present, although this effect was neutralised by the
presence of sufficient NaOH. Secondly, the amount of butanol which could be dissolved in the
aqueous phase was found to decrease as the amount of NaOH present increased but was largely
independent of the amount of HMD. Lastly, the partitioning coefficient of HMD was found to
decrease as the amount of HMD increased but increased as the molar ratio of NaOH to HMD was
raised. Fitted equations for these three findings allowed closure to be achieved. This model
predicted a set of operating conditions giving 99.95% extraction of a very dilute aqueous HMD
solution (1 wt%), including a doubling of the HMD concentration in the organic product.

Introduction

Hexamethylenediamine, hereinafter referred to as HMD, is an unbranched 6 carbon chain,

terminated at each end by an amine group. It is used in the production of nylon polymers, most
commonly Nylon-6,6, in which it is reacted with adipic acid. Due to the relative monetary
values of HMD and adipic acid, this reaction is done with a stoichiometric excess of HMD,
resulting in an aqueous waste which contains a low concentration of HMD [1], [2].

Methods for the recovery of low concentrations of HMD in aqueous solution have been
investigated because this separation is important in (i) reclaiming HMD from waste generated
in the production of nylon, (ii) extracting HMD produced biologically by fermentation, or (iii)
reclaiming it from waste emanating from the depolymerization of nylon, e.g. by ammonolysis.
The nature of HMD as an amine allows for methods of separation exploiting the variable charge
on the molecule: depending on the pH of the solvent, HMD can be either highly charged and
hydrophilic, or uncharged and hydrophobic. This paper builds upon previous work which
investigated methods of extracting HMD using pH and salt to cause a secondary phase to be
generated [3]. The present work includes the addition of an organic solvent, which is
immiscible with water, into which the HMD is preferentially extracted, following adjustment of
the pH of the feed stream. Final treatment of the raffinate stream remaining after the extraction
would depend to an extent on how it arose, viz. from a recycling operation or from a
fermentation stream. However, in the context of the current paper, the sodium hydroxide used
for pH adjustment would need treatment, probably by ion exchange, before discharge, the
details depending on other operations on the specific company site

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28/02/24 15.14 The separation of hexamethylenediamine from aqueous solution by solvent extraction with butanol - ScienceDirect

The study of amines in the field of solvent extraction is largely concerned with using the amine
as the secondary solvent with which to extract a solute from a primary solvent. Long chain
amines with low water solubility have been used for a wide range of solutes including rare
earth mineral ions [4], [5], [6] and organic acids [7], [8], [9]. However, the extraction of amines,
and diamines, as the solutes has been much less widely studied, although research has been
undertaken in which a membrane has been used to separate the liquid phases [10], or a dye has
been reacted with the amine prior to extraction [11].

This paper details an experimental campaign which used solvents to extract HMD from a dilute
aqueous mixture, to understand the thermodynamics of the phase equilibrium. The resulting
thermodynamic data were used to construct a model which could be used to predict the
performance of single-stage or multi-stage solvent extraction.

Section snippets

Materials and methods

As a diamine, HMD can exist in three different valence states, depending on the pH of the
solution. Fig. 1 shows the fraction of HMD present in each of these states, using the following
values of the dissociation constants: pKa,1 = 10.7 and pKa,2 = 11.02 [12].

Under neutral to mildly basic conditions, HMD is divalent and highly hydrophilic. However, if
the pH is raised high enough, the HMD loses its charge and becomes nonvalent, increasing its
affinity for hydrophobic solvents. The pH can be…

Solvent selection

The first experimental step was to determine which solvent should be used for the most
efficient extraction of HMD from the aqueous phase. To this end, preliminary experiments were
performed with a range of solvents. Each solvent was mixed in a 1:1 volumetric ratio with four
different aqueous solutions, containing either 50 or 90 g L-1 HMD, and either 0 or 3 equivalents
of NaOH. For these preliminary experiments, the characteristic by which the solvents were
measured was the partitioning…

Modelling the equilibria

The experimental results give an understanding of how the 4-component system reaches
equilibrium between aqueous and organic phases. These results were then used to construct a
model of the system, which could be used to investigate how butanol might be used practically
to extract dilute HMD from its aqueous phase.

Consider a single mixer settler as an equilibrium stage, as shown in Fig. 5. There will be a total
combined feed mass flowrate , which will have mass fractions , , , and …

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Multistage extraction

The experimentally-derived equilibrium equations (3), (4), (5) can be included in the model for
a single mixer-settler given at the start of Section 4. The model is now closed, as it contains 10
independent equations for the 10 unknown variables, and as such the equilibrium separation of
such a mixer-settler unit can be predicted. The model can therefore be incorporated into a
model of a multi-stage extraction process.

Fig. 9 shows a schematic diagram of a three-stage countercurrent solvent…

Conclusions

This work has investigated the extraction of dilute aqueous solutions of HMD using organic
solvents. A preliminary investigation showed that butanol would be a promising solvent, owing
to its polar and organic nature, which allows it to dissolve HMD readily, with a maximum
solubility for HMD of 78 wt%. Samples containing HMD, water, and butanol at various
concentrations were produced, and the mass fractions of all species in each of the aqueous and
organic phases were measured by gas…

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.…

Acknowledgements
The authors would like to thank INVISTA Textiles (U.K.) Limited funding for this work.…

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