Chapter 2: Literature Review

2.0 Introduction

Polystyrene (PS), one of the most used polymers in everyday life, has a low recycling rate due to
its inexpensive virgin resin. In order to make polystyrene waste (WPS) recycling advantageous,
it is possible to change it chemically, introducing heteroatoms in the polymer chain thus
transforming the waste into a material with more added value. In this work, sulfonation
reactions of polystyrene waste (disposable cups and expanded polystyrene -EPS) with different
degrees of sulfonation were carried out by homogeneous sulfonation using sulfuric acid in
formaldehyde as a sulfonating agent, originating polystyrene sulfonate (PSS).

2.1 Background

Plastic packaging is one of the most rapidly evolving and technologically sophisticated end used
for plastics. However, at the end of its useful life, plastic packaging are still seen as a problem
and their disposal has become an worldwide issue. The vast majority of PS packaging is
disposed of in landfills, waste dumps and sometimes even thrown into the ocean as disposal
method. Around 75% of all the litter in our oceans is plastic, and an estimated 5 million tons of
plastic waste enter the seas annually. An alternative to landfills, waste dumps and ocean
littering is incineration, which produces gases such as COx, NOx, SOx and polyaromatic
hydrocarbons (PAHs) that are toxic and carcinogenic. For the year of 2016 United States
consumed 1609 thousand metric tons of PS and less than 1% of it was recycled. For the last 15
years the recycling rate of polystyrene has never been above 1.2% and the estimates for the
next 5 years is that it remains constant at 0.9% [11-15]

According to ORMONDE et al.[13], nowadays, the main obstacle to plastic

recycling/reclamation is the continued low price of oil, the raw material from which plastics are
made. The authors suggest that in order to be successful the recycling industry must innovate,
integrate to add value and create new products and market.

As an effort to add value to polystyrene waste (WPS), an alternative for its recycling is to
change it chemically transforming the waste into a material with more added value. The
introduction of heteroatoms in the polymeric chain changes its physical, chemical and
mechanical properties and, consequently, its conductivity, hydrofilicity, solubility, acidity and
other properties. These properties can be customized to specific purposes6. Therefore, the
waste material is converted into a higher value substance.

Sulfonation of polystyrene, in other words, the insertion of acid sulfonic groups (-SO3H) in the
polymer chain, produces polystyrene sulfonate (PSS), a polyelectrolyte that can be used in a
wide range of applications. Unique properties arise from this modification of the polymer chain
and, by varying the degree of sulfonation in PSS, it is possible to tune the polymer's properties,
making it suitable for the desired application. This structure modification on the structure and
the possibility of controlling the polymer's new properties have led to an exploration of a
variety of applications, such as biocompatible electrodes [7], stimuli-responsive photonic
crystals[8] humidity sensors[19-20], components of photovoltaic devices ion exchange
membranes , flocculant material for water treatment and catalysts.

2.2 Sulfonation

Polymer sulfonation can be a heterogeneous reaction when the polymer and the sulfonating
agent are in different phases or a homogeneous reaction using hydrocarbons or chlorinated
solvents so that all the reactants are in liquid state. When the sulfonation of a polymer occurs
after its polymerization (as is the case of sulfonating a residue) and the reaction is conducted in
homogeneous medium, the solubility of the polymers (which is generally good in strong acids
and chlorinated organic solvents) and the solvent compatibility with other reactants are key
factors for the success of the reaction. An alternative to sulfonation conducted without these
solvents is a heterogeneous sulfonation. In this case, the polymer in its natural state (solid) is
immersed in a solution containing the sulfonating agent. As sulfonation takes place, -SO3H
groups inserted in the chain modify the material solubilization, and it becomes soluble in the
sulfonating agent solution and in this case heterogeneous sulfonation takes place

Sulfonated polystyrene resin

2.3 Resins in mineral processing

The historical use of sulfonated polystyrene resin in hydrometallurgy is interesting. As part of

the Manhattan project during World War II. Resins has since had a long history in nuclear
processing and many of the largest-scale operations are for uranium recovery. This industry
pioneered the development of resins for metal extraction, specialized contactors and novel
contacting approaches, such as resin-in-pulp (RIP). In the 1950s, resins received attention for
the recovery of gold from cyanide solutions; first reports of successful application came out of
the Soviet Union in the 1970s. With the advent of activated carbon and carbon-in-pulp (CIP)
technologies in the 1970s and 1980s, resin applications for precious metals recovery received
renewed attention and have since been steadily supported and advanced by researchers and
resin manufacturers.

Gold recovery involves primary extraction of the respective metals from dilute leach liquors and
takes advantage of the high upgrade ratios that are facilitated by the technology. More recent
applications, enabled by the development of highly selective and specialized resins, involve
scavenging applications in the base metals industry, where resins are used to recover low levels
of impurity metals from concentrated solutions, such as the removal of contaminating zinc and
copper from concentrated cobalt electrolytes prior to electrowinning (EW). Scavenging
applications are also increasingly relevant in the precious metals industry, where resins are
used to recover low concentrations of valuable components from spent process and waste
waters.

Knowledge has improved regarding the process and cost advantages that this technology can
provide in complex flow sheets. Modern resins can be highly selective and durable; in general,
the technical advantages at low metal concentrations in comparison with precipitation, solvent
extraction (SX), and membrane and activated carbon technologies. Furthermore, most
processes are inherently safe, owing to the low toxicity of the media, and pose negligible fire or
explosion risk.

This overview discusses some modern applications of sulfonated polystyrene in

hydrometallurgical processes, from primary recovery of gold, to complicated separation
schemes for precious metals, through to a growing number of scavenging applications. The high
value of the precious metals (Au, Ag, Pt, Pd, Rh, Ir, Ru, and Os) and their selectivity for resins,
coupled with shortcomings of traditional recovery and refining techniques. Many investigations
have been undertaken, but the number of successful applications is remarkably limited.

The presence of copper-bearing minerals is known to bring on many challenges during the
cyanidation of gold ore, like high consumption of cyanide and low extraction of metal, which
are undesirable impacts on the auriferous/ economic recovery in the subsequent process step.
The high copper solubility in cyanide prevents the direct use of classical hydrometallurgical
processes for the extraction of gold by cyanidation. Additionally, the application of a
conventional flotation process to extract copper is further complicated when it is oxidized. Also,
some other metals like nickel silver also have an effect on the convectional recovery method
that is hydrometallurgy using cyanide based lixiviant.

In primary applications, the need is to selectively and quantitatively recover low concentrations
of precious metals from leach liquors that usually contain high concentrations of base metals.
Many separation approaches, each with advantages and shortcomings, have been proposed
and implemented, including cementation, SX, IX, and adsorption on activated carbon.

Leaching of gold and silver from ores is typically carried out in cyanide solutions, and the
valuable metals are recovered from solution via the Merrill–Crowe zinc cementation process or
by adsorption on activated carbon in the CIP, carbon-in-leach (CIL), or carbon-in-column (CIC)
processes. Since the 1970s, there has been a great deal of research and implementation of
activated carbon processes due to its effectiveness and advantages. Activated carbon is highly
selective for gold and silver adsorption, and separation of the loaded carbon from the leach
pulp requires only a simple physical screen; however, interferences from so-called “preg-
robbing” ore constituents, such as organics and base metals, do occur. Additionally, stripping of
the precious metals from carbon is a chemical- and energy-intensive process. Activated carbon
also requires thermal regeneration at 600–700°C, which contributes significantly to operating
costs and in this study the presence of base metals in the ore gives rice to the shortcoming of
the use of activated carbon.

There are many of the advantages of activated carbon, such as direct adsorption of leached
metals from the pulp, high loading capacity, good selectivity and simple physical separations,
but there is no need for the elution to be carried out at high temperatures nor for thermal
reactivation. Resins are, however, more expensive than activated carbon and their particles are
smaller, requiring smaller-aperture screens to separate resin and pulp and hence a larger
screen area to achieve the same screening efficiency. Despite these drawbacks, the costs are
more than offset by the improved capacity and reaction kinetics of sulfonated polystyrene
resins over activated carbon [1].

Considerable research has been devoted to recovery of precious metals from cyanide solutions
[2-5]. The use of resins to recover Au and Ag from cyanide solutions goes back to the 1950s [3],
but the earliest success occurred in the implementation of RIP technology in the then Soviet
Union [2, 7]. Many research studies were carried out at Mintek (South Africa) to refine the
process, develop new resins, and improve stripping [3-6].

Two resin functionalities are advocated for gold recovery from cyanide leaching—strong-base
and weak-base resins. Strong-base resins incorporate quaternary amine groups with a
permanent positive charge: they show no pH dependency and will adsorb gold from solution,
even at very high pH levels. However, this same lack of pH dependence makes these resins very
difficult to strip: the elution process invariably involves displacement of the aurocyanide anion
with a base metal cyanoanion, or conversion of the loaded aurocyanide anion into a cationic
species with no resin affinity. In contrast, weak- or medium-base resins have primary,
secondary or tertiary amine functional groups that first require a protonation step to create
functionality, before loading can take place [9]:

Stripping of these resins is straightforward, involving deprotonation by contact with alkaline

solution:

These reactions give these resins their distinctive pH functionality: high loadings at low pH
values and low loadings at high pH values. Because gold is leached in cyanide at high pH
[necessary to avoid the production of deadly hydrogen cyanide (HCN) gas], use of weak-base
resins often involves a compromise between the pH of loading, the degree of gold extraction,
and the extent of resin loading.

Much of the early investigative work on RIP technology involved generic, commercially
available strong- and weak-base resins [4, 5]; however, research evolved to the development of
specialized resins for specific applications, which has led to some important commercial
applications [6-8]. In 1999, the Penjom Mine in Malaysia, at that time owned by Avocet Mining,
implemented an RIL process using a specialty resin developed by Mintek and manufactured by
Dow [10]. The strong-base resin contains tributylamine functional groups, the loading reaction
for which is given as [6]:

The loaded resin is first stripped with H2SO4 to remove any absorbed base metal; gold is then
stripped using an acidic thiourea (TU) solution to convert the anionic aurocyanide complex to a
cationic thiourea complex:

HCN evolved during the acidic stripping processes is recovered in an alkaline scrubber and
returned to the leach circuit.

Mintek’s strong-base resin has also been used at the Gedabek gold and copper deposit in
Azerbaijan [9]. Purolite’s medium-base resin, S992, has been implemented in an RIP application
at Petropavlovsk’s Pioneer gold mine in Russia [11]. Both of these resins offer high selectivity
for gold from solutions containing very high copper concentrations [12]. Medium-base resins,
such as AuRIX® 100 that contains the guanidine functional group, have been prepared and
studied but have seen limited application due to resin costs.

The eluates from activated carbon can be contacted with a sulfonated polystyrene resin to
reabsorb the precious metals, which can then stripped into a highly concentrated solution that
can be treated by a simple precipitation process, such as copper cementation, to produce a
high value product suitable for direct shipping to a refiner.

The recovery of gold and silver from its minerals is achieved by liberation of the metal values by
dissolution in alkaline solution of cyanide salts. In the last years the exhaustion of rich minerals
is forcing to the application of hydrometallurgical techniques to the recovery of noble and
precious metals from dilute ore sources. For example, dump, heap and vat leaching of selected
ores are employed commercially. The gold mining industry practiced great implantation of ion
exchange resins (IX) recovery processes. Cyanidation leaching steps are combined with
subsequent steps of gold cyanide adsorption with activated carbon (AC). In the last years,
research efforts have attempted substitution of AC by synthetic solid ion exchange resins and
solid polymeric adsorbents.

Synthetic solid ion exchange resins seem to have an economic edge over carbon adsorption in
certain applications, viz., calcined/clay ores, small operations, and organic-contaminated
process streams. The history of applying IX technology in the processing of gold cyanide
containing alkaline liquors dates back to the earliest 1950's - the period during which the zinc-
dust precipitation method was the industry standard. Since then, there have been sporadic
bursts of activity in a number of laboratories around the world. Recently, however, an
increasing number of studies have considered IX as a potential alternative to the well-
established processes of activated carbon adsorption and zinc-dust precipitation. Commercially
available resins were unable to compete with activated carbon (AC) due to poor selectivity,
mechanical breakdown of the beads and the requirement for complex elution and regeneration
processes following different routes than those used with AC. Yet, IX resins offer some chemical
advantages over activated carbon and have excellent technical potential for application in gold
extraction systems.

The main objective with the use of synthetic solid polymeric adsorbents is to solve existing
problems associated with the use of activated carbon by improving the selective recovery of
gold cyanide, to increase loading and stripping efficiencies, and to develop integrated process
of leaching and extraction as resin-in-leach (RIL) and resin-in-pulp (RIP).

Since typical gold leaching solutions contain gold as Au(CN)2 " and other metal cyanides such as
Ag, Fe, Cu and Ni at pH>10, these objectives might be accomplished by developing synthetic
solid adsorbents with a suitable functional group that can extract precious and noble metal
cyanides.

A variety of such solid extractants are known. In initial attempts, described in the literature,
gold was adsorbed and eluted effectively using strong base anion exchange resins. However to
overcome the high binding energy of strong base resins for the aurocyanide ion, elution
required the use of thiourea, thiocyanate, zinc cyanide, and/or polar solvents. The resin must
then be regenerated with acid prior to recycling. This type of elution/regeneration is complex
and expensive. It would be highly desirable to apply weak base resins ( WBR) to extract gold,
since WBR can be eluted by simply shifting the pH to higher values and reverting the gold
cyanide binding reaction. Such weak-base anion exchange resins could be applied if the
functional group is protonated. This acid-base equilibrium is readily reversed by alteraing the
solution pH converting the resin back into its free base form at pH values around 6-8. As the
cyanide leach streams have pH values of around 10-11 this is simply inadequate. As a result
only a small percentage of the amine groups in standard weak base resins are protonated in the
leach stream and very low exchange of the aurocyanide occurs. Hence commercially available
WBRs were found to possess low gold loading capacity due to those low pKa values.

Efforts have, therefore, been made to develop resins with high pKd values to allow the
extraction of gold at the natural pH of a cyanide leach solution (9-10). New weak base anion-
exchange resins, containing primary, secondary and tertiary amine functional groups, have
been synthesized for the recovery of gold from cyanide solutions.

2.5 Summary Of The Invention

It is an object of the present invention to provide new ion exchange resins that overcome the
disadvantages of the prior art for the selective extraction of gold, silver, copper or any metal
cyano-complexes.

It is a further object of the present invention to provide new ion exchange resins that are
particularly efficient for the selective extraction of gold cyanide complexes.

Thus, according to the present invention, sulfonated polystyrene resin was selected as a
candidate for the development of suitable resins for gold cyanide extraction from cyanide
solutions by functionalizing the polystyrene so as to create an ion exchange ability on the non-
biodegradable plastic with macroporous polymeric supports.

The present invention thus relates, in one aspect, to an ion exchange resin composed of a
polymeric matrix functionalized with a sulfonate group.

The ion exchange resin may have a polymeric matrix based on a polystyrene or
polymethacrylate polymer and copolymers thereof, or on any other aromatic or aliphatic
polymer containing electrophilic groups that can be readily reacted with sulfonic acid or sulfuric
acid in formaldehyde as the binding agent.

In one preferred embodiment, the ion exchange resin is based on a polystyrene copolymer,
more preferably on a polystyrene-divinylbenzene copolymer. In another preferred
embodiment, the ion exchange resin is based on a polymethacrylate copolymer, more
preferably on a poly[(glycidyl methacrylate)-co-(ethylene dimethacrylate)].
In another aspect, the present invention provides a process for separating gold cyanide
complex from an aqueous medium containing a mixture of other metal cyanide complexes,
which comprises contacting said aqueous medium with a sulfonate functionalized ion exchange
resin of the invention, whereby said gold cyanide complex is preferentially retained on said
sulfonate functionalized ion exchange resin. In one preferred embodiment, the resin is of the
formulas shown above.

According to this aspect of the invention, the process may comprise the additional steps of
rinsing the resin, e.g. with water, to remove excess of retained solution, and eluting the gold
cyanide complex. Elution may be carried out with thiourea, NaOH or NaOH in a solvent such as
ethanol, acetone, DMSO or the like. For recovery of gold, the preferable eluant is a solution of
sodium hydroxide in ethanol, more preferably a solution of about 40g/L NaOH in 40% ethanol.
Gold can then be recovered from the eluted material by methods well-known in the art.

In another embodiment, the invention relates to a process for separating gold and silver
cyanide complex from an aqueous medium containing a mixture of other metal cyanide
complexes, which comprises contacting said aqueous medium with an ion exchange resin of the
invention, whereby said gold cyanide and silver cyanide complexes are preferentially retained
on said sulfonate functionalized ion exchange resin. For recovery of the gold and silver cyanide
complexes, elution is preferably carried out with thiourea, more preferably a solution
containing 1 M thiourea and 1 M sulfuric acid.
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