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Sohn International Symposium ADVANCED PROCESSING OF METALS AND MATERIALS

VOLUME 3 - THERMO AND PHYSICOCHEMICAL PRINCIPLES:


SPECIAL MATERIALS and AQUEOUS AND ELECTROCHEMICAL PROCESSING
Edited by F. Kongoli and R.G. Reddy TMS (The Minerals, Metals & Materials Society), 2006

INTERFACIAL EMULSION FORMATION ORIGINATED FROM


ORGANIC PHASE IN COPPER SOLVENT EXTRACTION
Xiaorong Liu1, Guanzhou Qiu2, Yuehua Hu2

1. Department of Materials Engineering, Shanghai Institute of Technology,


Shanghai 200233, P.R.China
2. Department of Mineral Engineering, Central South University
Changsha 410083, P.R.China

Keywords: interfacial emulsion, emphiphiles, degradation, copper solvent extraction.

Abstract

Interfacial emulsion generated in copper solvent extraction is an inhomogeneous O/W emulsion


that consists of organic phase, aqueous phase and solid particles. In order to determine what kind
of components in organic phase promotes the emulsion, the organic phase separated from the
interfacial crud provided by Dexing Copper Mine in Jiangxi, China was analyzed for its
components by combined gas chromatography-mass spectroscopy. It was found that many kinds
of emphiphiles containing such hydrophilic groups as carbonyl, carboxyl, or acylamine existed in
organic phase, most of which were originated from the reagent degradation.

Conclusively, Lix984N would degrade gradually during a long-term contact with the acidic
aqueous feed and strip reagents. Lix84 and nonylphenol, as effective components of Lix984N,
degraded almost completely after long-term recycling. As a result, the effective components of
Lix984N were far lower in concentration than the dense-aromatic impurities derived from the
diluent and the degradation products in total. The degradation of Lix984N would deteriorate
solvent extraction, disengagement performance and result in more serious interfacial emulsion.

Introduction

Developing more than 30 years, Copper solvent extraction tends to be a more and more perfect
hydrometallurgical technology. However, many kinds of problem often emerge out in practiced,
within which interfacial cruds are supposed to be one of the commonest and most troublesome.
Generally, interfacial cruds are inhomogeneous O/W emulsions that consist of organic phase,
aqueous phase and solid particles. It can lead to a lot of detrimental effects to plant operations
including difficult phase disengagement, contaminated electrolytes, extractant loss, declined
product quality and polluted environment. Loss of control over interfacial emulsions formation
can even cause plant shutdown [1].

Dexing Copper Mine is the first plant in China using the technology of bioleaching-solvent
extraction -electrowinning to extract copper hydrometallurgically. The serious interfacial cruds
created in extraction operation at the beginning of running ever made adversely the whole
process run in a deteriorated situation. Controlling over the crud formation turns to be crucial to
the whole hydrometallurgical process.

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Emulsions are unstable thermodynamically. Actually, they can be stable dynamically depending
on one or more following mechanism: low liquid-liquid interfacial tension [2], liquid crystal
phase formation [3], electrostatic repulsive force between droplets [4,5], interfacial solid films
[6,7,8] and structural stabilizing effects [9]. According to previous researches, the presence of
surface-active constituents in the organic phase, suspended solids or colloids in the aqueous feed
and three-dimensional structure existed in the emulsions was mostly related to stably forming of
the interfacial emulsion in Copper solvent extraction [10]. The surface-active constituents in
organic phase definitely consisted of the impurities and degradation products of the alkaryl
hydroxyoxime reagents, Lix984N, used in Copper solvent extraction.

Contacting with the acidic aqueous feed and strongly concentrated strip reagents permanently
and being accessible to sunlight, the hydroxyoxime reagents degrade gradually in the process
circuits via such chemical reactions as hydrolyzing, redox reacting, isomerizing, photolyzing, etc
[11,12,13]. The degradations of organic component are complicated in the plant operations. In
fact, every kind of oxime reagent has its own degrading ways and mechanisms. There are too
short of correlative researches to explain clearly how the reagents degrading in copper solvent
extraction up to the present. But it is true that the degradations absolutely destroy the
hydroxyoxime functions of the reagent and produce surface-active constituents. So, degradation
of Lix984N would deteriorate solvent extraction and disengagement performance and result in
more serious interfacial emulsion.

In order to eliminate or control stable emulsion formation at the liquid interfaces, it is necessary
to find out what leads to stable emulsions, or how the interfacial emulsions are stable. Using
combined gas chromatography-mass spectroscopy (GC-MS), a lot of analyses were made to
identify the components in the organic phase extracted from copperSX circuit cruds from
DeXing Copper Mine. It is helpful to understand how Lix984N degraded in copperSX process
and to reveal the primary causes of interfacial crud formation.

Experimental Methods

Materials

Crud samples, commercial 260# kerosene used as diluent, recycling loaded organic sample and
commercial Lix984N were obtained from the copper solvent extraction plant of DeXing Copper
Mine in Jiangxi, China. Strip reagents with the concentration of 160 g/L H2SO4 were prepared
with CP grade salt CuSO4y5H2O and sulfuric acid. CP grade reagents and distilled water was
used throughout.

Methods

Acetone Extraction of Crud. Making use of the methods of reference [11], crud samples (30ml)
were loaded into 50ml centrifuge tubes, then centrifugalized at about 9000 rpm for 1 hour at 26
. After centrifugation, samples exhibited a waxy semi-solid phase between an aqueous phase at
the bottom and a dark organic phase at the top. This waxy semi-solid phase mainly consisted of
organic compounds and inorganic particulates. A portion of waxy semi-solid phase (6g) was
resuspended by agitation with acetone (20ml) and again centrifugalized. This procedure was
repeated three times on one sample to strip organic compounds from inorganic particulates.

The organic liquid striped from the inorganic particulates of waxy semi-solid phase was denoted
as OCS. The loaded organic phase long-term used in practice was denoted as LO and SO
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represented the organic phase stripped from LO with strip reagents of 160 g/L H2SO4.

Combined Gas Chromatography-Mass Spectroscopy. The commercial 260# kerosene, Lix984N,


OCS, LO and SO were identified by combined gas chromatography-mass spectroscopy of model
HPGC-MSD5917. A polyethylene glycol capillary column of 25m was used for identifying polar
components. Helium was used as the carrier gas with a pressure of 4PSI. The injector
temperature was 250. The oven temperature was linearly raised by 2.5/min from 140 to
210. The spectrometer was operated with an energy setting of 70 eV.

A polymethylsiloxane capillary was used for identifying unpolar components in the kerosene.
The oven temperature was linearly raised by 5/min from70 to 220. The other conditions
were same with the above-mentioned.

Results and Discussions

GC-MS analysis of OCS

A total ion flow gas chromatogram of OCS was shown in Figure 1. Two clusters of different
category of compounds were observed, which were concerned as dominating components
resulting in stable emulsion formation. The GC peaks between retention times 5 min and 12 min
marked as 1, 2, 3 were identified by the GC-MS as methylnaphthalene, dimethylnaphthalene and
trimethylnaphthalene, respectively. The total concentration of dense-aromatic compounds was
obviously higher than that of compounds in another cluster marked D. The relative proportions
of methylnaphthalene, dimethylnaphthalene, trimethylnaphthalene in dense-aromatic compounds
according to MS results were 52.3%, 37.5% and 10.2%.

1 2

2 D

3 33

retention time / min


Sample volume: 0.6 L
1: methylnaphthalene 2: dimethylnaphthalene
3: trimethylnaphthalene
Cluster D: isomers of unkwon emphiphiles
Figure 1 Total ion flow gas chromatogram of OCS

The cluster D covered many complicated components, all of which were supposed to have the
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following similar phenyl structure according to their ion abundances.

Y was thought primarily as hydroxyl in most components of the cluster D and X might represent
carboxyl, carbonyl or acylamine in different components respectively. More analysis had to be
done to identify the components of cluster D completely. Obviously, they were surface-active
emphiphiles and dominating sources to formation and stability of the interfacial emulsion. In
order to ascertain where the dense-aromatic compounds and the emphiphiles originated from,
commercial diluent and Lix984N reagent was analyzed for their compounds by GC-MS.

GC-MS analysis of commercial 260# kerosene

The total ion flow gas chromatogram of commercial 260# kerosene was shown in Figure 2. The
identified results were listed in Table 1. It was proved that the dense-aromatic compounds in the
OCS originated from the diluent. These impurities came from the kerosene processing from
petroleum refining and accumulated in the long-term used organic phase.

retention time / min


Sample volume: 0.5 L
Figure 2 Total ion flow gas chromatogram of the diluent

Table I. Identification of the GC of commercial 260# kerosene


Peak no. Identification Relative content/%
1 Undecane 82
2 Decane 500
3 2,6 dimethyl- undecane 179
4 degradation compounds of Lix84 21
5 epoxynonane 14
6 epoxydecane 14
7 Naphthalene 0.9

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8 Methylnaphthalene 51
9 7-methyltridecane 35
10 Dimethylnaphthalene 12
11 Pentadecane 84

GC-MS analysis of Lix984N

Lix984N, one of the most effective reagents for copper solvent extraction, is a mixture of
2-hydroxy-5-nonylacetophenone oxime and 5-nonylsalicylaldoxime, which is the effective
component of Lix860N and Lix84, respectively, in a high flash diluent.

In Figure 3 the total ion flow gas chromatogram of Lix984N was shown. The cluster marked as 5
included the peaks corresponding to effective components of Lix84, and the cluster marked as 7
included that of Lix860N. Apparently, the cluster marked as 6 covered the peaks corresponding
to effective components of 4-nonylphenol, which works as the modifier in Lix984N. Three main
effective components in Lix984N are the mixtures of their isomers. The peaks marked as 1, 2, 3,
4, respectively corresponded to 1-ethyl 4-(1-methylethyl) benzene, 1-(2-hydroxy)-acetophenone,
2-Ethyl hexoic acid and phenol, which were some impurities left in Lix984N and might cause
some adverse effects on interfacial emulsion formation because of their surface-activity. No
components same as that in OCS could be found in the extractant.

Compared Figure 1 with Figure 2 and Figure 3, it was clear that methylnaphthalene,
dimethylnaphthalene and trimethylnaphthalene were brought into organic phase by the diluent
and then accumulated in the interfacial cruds. The components of the cluster D between 16 min
and 24 min of retention time in Figure 1 were not brought by Lix984N and the diluent. These
surface-active components enriching in OCS /or the interfacial emulsions came into being during
the extraction process and result absolutely from the degradation of the extractant.



 
1
 
     


retention time / min


Sample volume: 0.6 L
1: 1-ethyl 4-(1-methylethyl) benzene 2: 1-(2-hydroxy)-acetophenone
3: 2-Ethyl hexoic acid 4: phenol
Cluster 5: isomers of 5-nonylsalicylaldoxime
Cluster 6: isomers of 4-nonylphenol
Cluster 7: isomers of 2-hydroxy-5-nonylacetophenone oxime
Figure 3 Total ion flow gas chromatogram of Lix984N
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GC-MS analysis of LO and SO

The total ion flow gas chromatogram of LO was shown in Figure 4 and that of SO in Figure 5.
Compared their ion abundances with each other, the components corresponding to the peaks
marked as 1, 2, 3 and in the cluster D in two figures seemed to be same. Noticeably, the most
obvious difference between the components of LO and SO was that the effective components of
Lix860N appeared in SO after stripping. At the same time, the effective components of Lix84
and 4-nonylphenol did not appeare in the stripped recycling organic phase. It can be judged
definitely that they degraded completely after long-term recycling and their stabilities were
worse than that of Lix860N. As a result, the effective components of the extractant were far
lower in concentration than the dense-aromatic impurities derived from diluent and the
degradation products in total.

D
2 3 33

retention time / min


Sample volume: 0.8 L
1: methylnaphthalene 2: dimethylnaphthalene
3: trimethylnaphthalene
Cluster D: isomers of unkwon emphiphiles
Figure 4 Total ion flow gas chromatogram of LO

The components between 16 min and 24 min of retention time in Figure 1, Figure 4 and Figure 5
seemed to be the same according to GC-MS analysis. It could be deduced that these compounds
were degradation products from Lix84 and the modifier. Conclusively, Lix984N will degrade
gradually during a long-term contact with the acidic aqueous feed and strip reagents. Lix84 and
nonylphenol, as effective components of Lix984N, degraded almost completely after long-term
recycling. Such impurities as 1-ethyl 4-(1-methylethyl) benzene, 1-(2-hydroxy)-acetophenone,
2-Ethyl hexoic acid and phenol existing in Lix984N degraded too.

Meanwhile, OCS was stripped with the strip reagent and then analyzed by GC-MS, too. It was
found that the total ion flow gas chromatogram of stripped OCS tended to be the same with that
of OCS and the effective components of the extractant could not be found. This implied that the
copper/extractant complexes would not be adsorbed at surfaces of the inorganic particles in
interfacial emulsion. Certainly, the effective components of Lix984N would not too. The organic
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components adsorbed at surfaces of the inorganic particles in interfacial emulsion just included
dense-aromatic impurities derived from the diluent and the degradation products of Lix984N.

These surface-active constituents accumulating in the organic phase would make interfacial
tension lower. On the other hand, the polar groups of the constituents combined with the active
centers on the surfaces of inorganic particles, for example forming hydrogen bond and,
ultimately, promoted solid interfacial complex film forming on the droplet surfaces, as shown in
Figure 6. The interfacial complex film had stronger effects on stabilizing droplets and in
succession interfacial emulsions because of the cooperating effects of emphiphiles and inorganic
particles. So it was these surface-active emphiphiles that promoted interfacial emulsion forming
and made them stable.

333 Isomers of Lix860N

retention time / min


Sample volume: 0.5 L
1: methylnaphthalene 2: dimethylnaphthalene
3: trimethylnaphthalene
Cluster D: isomers of unkwon emphiphiles
Figure 5 Total ion flow gas chromatogram of SO

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Acknowledgements

The authors wish to acknowledge support received from Shanghai Leading Academic Discipline
projects P1502.

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