Hydrometallurgy 50 1998.

121

Organic constituents of cruds in Cu solvent

extraction circuits.
I. Separation and identification of diluent-soluble
compounds
)
R.P. Sperline, Y. Song, E. Ma, H. Freiser
Strategic Metals Recoery Research Facility, Department of Chemistry, Uniersity of Arizona, Tucson, AZ,
85721-0041, USA

Received 1 December 1997; revised 20 April 1998; accepted 25 April 1998

Abstract

Interfacial cruds from hydrometallurgical solvent extraction of copper ions were examined to
assist in the establishment of potential causes of cruds. Diluent-insoluble, polar organics com-
prised the majority of the solid mass of crud; inorganic particulates and bacterialrfungi were not
dominant. Procedures involving ultracentrifugation and acetone extraction were developed to
separate these cruds into inorganic, soluble organic, and insoluble organic fractions, and were used
to analyze 12 assorted extraction stage and strip stage cruds. UVVisible and infrared spectro-
scopic comparisons of the materials with known standard alkarylhydroxyoxime AAHO. reagents
and hydrolysis products were made. Two cruds were further examined by thin layer chromato-
graphic TLC. separation. Cruds contained larger proportions of de-oximated AAHO than did the
supernatant organic phase. Strip stage cruds contained more de-oximated AAHO, relative to the
AAHO reagents, than did the respective extraction stage cruds. Cruds contained larger proportions
of aliphatic carboxylic acids and aliphatic carboxylic esters, than did the respective supernatant
organic solutions. Copper complexes of AAHO reagents were not concentrated in the crud. The
polarity of the diluent-insoluble organics was reflected in TLC behavior. Diluent-insoluble
organics contained large amounts of carboxylic acids and esters. In experimental trials of the
reconstitution of crud from decanted organic and aqueous phases, added diluent-insoluble organics
obtained from crud were required for the reconstitution of crud, whereas inorganic particulates

)
Corresponding author. Fax: q1-520-621-8407; E-mail: freiser@shiva.ccit.arizona.edu

0304-386Xr98r$ - see front matter q 1998 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X 9 8 . 0 0 0 3 6 - X
2 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121

were not required. Inorganic particulates were incorporated into the reconstituted crud, but did not
reconstitute crud in the absence of diluent-insoluble organics. It was hypothesized that low-polar-
ity, diluent-soluble compounds are less likely to cause crud episodes, or even to be accumulated in
crud, than are the diluent-insoluble organics. q 1998 Elsevier Science B.V. All rights reserved.

Keywords: Crud; Diluent-soluble compounds; Solvent extraction

1. Introduction

In hydrometallurgical solvent extraction recovery of metals, a heterogeneous, partly

inorganic, partly organic mass of material accumulates at the interface between organic
and aqueous solutions. This crud, also known variously as gunk, gunkies, etc., can
be detrimental to plant operations. Loss of control over crud can lead a variety of
difficulties including contaminated product, loss of reagent, and complete failure of
phases to separate and plant shutdown. Knowledge of the composition, causes, and
methods of control over crud, therefore, is vital, yet is relatively unavailable in the
literature.
The most desirable result obtainable for a crud project would be elimination of, or
control over, the sources. of the compounds which lead to crudadmittedly a
formidable task. Development of control can proceed in three stages. 1. What com-
pounds constitute crud? 2. The sources. of the compounds must be tracked. Are they
introduced through contaminants in the reagents or in aqueous feed solutions? Are they
decomposition products of the reagents or solvents? Do cruds require the presence of
certain particles and where did they come from? 3. Can the sources or mechanisms of
compound introductionrformation be discovered and controlled? The present work
represents the first of a series of experiments designed to determine the chemical
composition of copperralkarylhydroxyoxime AAHO. SX cruds and to examine mecha-
nisms for their formation.

1.1. Background

The presence of finely divided silica has long been blamed for the generation of crud,
partially because hydrophilic particulates, especially kaolin, are known to stabilize
emulsions w16x and partially because silica and clay particles are found in the SX of
many different metals. Clarification of feed leach solutions remains a very important
aspect of crud control w7x. The presence of particular cations has been investigated w8x.
Humic acids have been impugned as contributing to crud difficulties w9x, although
addition of humic acid to a uranium-SX system did not produce stable crud w10x.
Isodecanoic acid from isodecanol modifier oxidation. was shown to contribute to crud
in uranium-SX w10x. An insoluble trialkylammonium phosphomolybdate was discovered
as the major component in molybdenum-SX crud w11x. Ritcey w12,13x has suggested that
hydrolyzed reagents in certain circuits can contribute to crud, a possibility we have
explored here, for copper-SX.
 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121 3

Previous descriptions of crud have been predominantly phenomenological, or have

examined the influences of known additives, e.g., finely divided silica, to clean systems.
The addition of particles of various materials to model systems does not, however,
reproduce the behavior of crud in actual extraction circuits. In uraniumrthorium
extraction, certain problematic cruds have been analyzed for the presence of particulates
arising from precipitation of degradation products of the reagents with the metal ions
w14,9,10,14x. Cruds in the widely utilized copper solvent extraction circuits have been
analyzed extensively for morphology and microbiologicals w15x, and metals composition,
but not to determine the actual chemical components present beyond the presence of
humic acids, lignins, and carboxylic acids.
A number of studies have recently been carried out on copper extractants w5,6,16x.
Clay treatment of recycled organic solution reduced crud formation w17x. Some reduction
of crud formation is obtained by the addition of surfactants to change the wetting
properties of clay particles w18x.
The behavior of crud is quite variable, changing from system to system, naturally, but
also changing with time in a given system. If the crud forms a stable blanket between
the solutions, it can actually assist in droplet coalescence. All too frequently, however,
crud can become mobile in either phase, leading to loss of extractant to the aqueous
raffinate, or to contamination of subsequent processing stages including the stripping
and electrowinning stages. The root causes of the changeover from stable to mobile crud
behavior are, as yet, unknown.
The published procedures for analysis of crud particulates include washing of the
cruds with acetone and collection of the particulates w15,19x. The acetone, presumably,
was discarded. This suggested to us that the acetone extract of copper-SX crud should be
analyzed, not only to determine the relative masses of insoluble organics and inorganics
in crud, but to determine the nature and identity of the organics. It did not seem
reasonable that either the volume or the viscosity of crud could be stabilized only by
inorganic particulates. In the case of copper-SX, at least, analysis of the acetone extract
has justified our skepticism. In general, the vast majority of the solid in crud in
copper-SX circuits utilizing AAHOs was found to be not silica or clay, but organic
material which was soluble in acetone but insoluble in both aqueous and diluent
solutions.
This paper details the separation methodology and the preliminary identification of
components obtained from copper-SX circuit cruds by comparison of IR and UV spectra
and chromatographic retention factors R f values. with those of reference materials. It
also outlines a demonstration that insoluble organic components insoluble in both
aqueous and diluent phases. were required to produce crud in copper-SX using AAHOs.

2. Experimental section

2.1. Materials

Distilled water and reagent grade solvents were used throughout. 5-Dodecylsalicy-
laldoxime DSAO, 96%., 5-nonyl-2-hydroxy-acetophenoneoxime HNAPO, 98%., do-
4 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121

decylsalicyladehyde DSA, 100%., and 5-nonyl-2-hydroxy-acetophenone HNAP, 98%.

were donated by Henkel, Tucson, AZ. 2,2,4-Trimethyl-1,3-pentanediyl diisobutyrate
TXIB, PM 1315., p-nonylphenol p-NP, 98%., and salicylaldoxime SAO.; Eastman
Chemical. SX-7 diluent, Phillips Chemical. Naphtha Nap, Technical., 1-naphthaldehyde
Nap-ald., and naphthenic acid Nap-acid.; Chem. Service. 2X-Hydroxyacetophenone
HAP, 99%., and salicylaldehyde SA, 98%., benzoxazole BX, 98%., 1,2-benzisoxa-
zole BIX, 95%., 2-methylbenzoxazole MBX, 99%., 2,5-dimethylbenzoxazole DMBX,
99%.; Aldrich.
Crud samples were obtained through Henkel, Tucson, AZ, from SX operations in
Arizona and in Chile South America.. All of these SX operations used DSAO or
DSAOrHNAP mixtures. One sample from Chile contained TXIB as a modifier.

2.2. Ultracentrifugation

Decanted gelatinous crud was loaded into 50-ml Oak Ridge-type sealed centrifuge
tubes. They were allowed to settle briefly and excess liquids were decanted. Polypropy-
lene copolymer tubes were used in the presence of acetone; polycarbonate tubes were
used otherwise. A Sorvall Instruments SS-34 rotor was used in a Serval refrigerated
ultracentrifuge. Samples were spun at 10,000 rpm for 13 h at 25288C.
After centrifugation, both extraction- E . and strip- S . stage cruds exhibited a
semi-solid dilatant phase at the bottom solidrwaxy, ; 20 vol.%., an aqueous phase
above that ; 3040 vol.%., and a dark organic phase at the top ; 3040 vol.%..
Dilatant phases increase in viscosity with increased sheer rate, the opposite of
thixotropic behavior. Often a second semi-solid dilatant phase also solidrwaxy, ; 20
vol.%. appeared between the aqueous and organic liquid phases. The solids were
collected by scooping and decantation. Both solid fractions fractured dilatant. upon
probing with a spatula. The S cruds gave a larger volume of upper solid when fresh than
after they had been allowed to stand for several days.

2.3. Acetone extraction of crud solids

A portion of the solid fraction from ultracentrifugation 1015 ml. was resuspended
by mechanical agitation and ultrasonication with acetone 40 ml. and again ultracen-
trifuged. This procedure was repeated six times on one sample of the solid to
exhaustively strip organic compounds from any inorganic particulates. The acetone
supernatants were combined and acetone removed under vacuum in a rotary evaporator.
The residual solids were collected and dried in vacuo at 608C.
During acetone evaporation, the solution separated into three phases: 1. a bottom
sticky, solidrwaxy solid, 2. an aqueous solution layer, and 3. an organic solution
layer. We will designate the organic solid 1. as acetone-off solid AOS. and the
organic solution 3. as acetone-off liquid AOL.. E stage cruds yielded AOS, aqueous
solution, and AOL in approximately 1:1:10 volume ratio. In S stage cruds this ratio was
approximately 1:1:1.
 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121 5

In subsequent analyses, the two solid layers from ultracentrifugation exhibited

essentially identical insoluble organic components in the same ratios. The concentrations
of inorganic particulates, however, were different. After extraction with acetone, both E
and S stage bottom solids were shown to contain 35% inorganic particles by weight,
whereas the upper solids from the E and S stage cruds contained 15.5% and 25%
inorganic particulates, respectively. S stage upper and bottom solids were similar
enough that only the upper solid was further analyzed. For the E stage cruds, the upper
and bottom solids were combined for subsequent analyses: further discussion will only
refer to one solid phase. On average, 40 ml of original gelatinous crud gave 2.6 g of
inorganic particulates, or approximately 6 wt.%.

2.4. Thin layer chromatography (TLC)

The TLC plates used were Analtech fluorescent Silica Gel GF, a. 20 = 20 cm, 1000
m thickness; and b. 5 = 10 cm, 250 m thickness for preparative separations and
preliminary tests, respectively. The plates were first eluted with acetone to remove any
trace organics on the plates before use. The mobile phase, determined by preliminary
screening tests, was a mixture of heptane and 1,2-dichloroethane DCE. 1:1 vrv.. In
order to get enough sample to identify, about 30 droplets ; 0.014 ml each. of solution
were applied in a line near one end of the plate. A UV lamp 254 nm wavelength. was
used for examination of the plates. Some fraction bands could not be observed under
UV, but gradually became yellow to the eye when exposed to air overnight. The
distances traveled by the solvent front and by a chromatographic band or spot from the
location of application were measured and the ratio of the distances reported as R f for
each band or spot.

2.5. Preparatory TLC

After elution, the loaded silica gel was scraped off the preparatory scale plates and
collected. Acetone was used as a solvent to extract =3. the loaded fractions from the
silica gel, with centrifugation. After evaporation of the acetone, the remaining material
was visible and usually oilyrwaxy. TLC immobile fractions were soluble in neither
heptane nor water. Each isolated, dried mobile fraction was dissolved in 0.5 ml heptane
for transmission IR spectroscopy. The solution was diluted further with heptane for UV
spectroscopy.

2.6. Spectral measurements

UVVisible spectra were obtained in 1.00 cm type Q silica cuvets, blanked against
heptane solvent, using a Hewlett-Packard HP 8452A Diode Array Spectrometer. Solu-
tion IR spectra were obtained using 0.050.1 mm pathlength solution cells with CaF2 or
KBr windows. The cell and spectrometer have been described elsewhere w20x. Suitable
6 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121

solid samples were ground with KBr and pressed into pellets for IR transmission
spectroscopy. Other solid samples were dissolved in volatile solvent and the solutions
evaporated on KBr or CaF2 plates to deposit the solids in thin films for IR analyses.
Spectra were plotted with Quattro Pro 4.0 Borland..

2.7. UV spectra

Solutions were made from preparatory-scale TLC fractions by extraction of the

thick-layer TLC plates after elution. UVVisible spectra of the fractions of cruds
S1-a(8-13), S1-ai(8-13), E1-a(2-19), and E1-ai(2-19) were obtained and compared with
spectra of solutions obtained in a similar fashion from AAHOs and other known
reagents. The initial plant organic solutions IOL. are indicated by ai and the AOL
organic solutions acetone-off liquid from extraction of crud with acetone. are indi-
cated by a. Fig. 1 shows these spectra for crud S1-ai(8-13), and Fig. 2 shows the
corresponding IR spectra of these solutions. These comparisons were typical of all four
cruds, so the others are not shown. For example, fraction 3 of the initial plant organic

Fig. 1. UVVisible transmission spectra of fractions of the initial plant organic phase supernatant to crud
S1-ai(8-13) and of matching fractions of reference compounds. Both crud and reference compounds were
separated by TLC on silica gel using heptanerdichloroethane eluant. Fractions dissolved from the TLC plate
into heptane. Key: solid lines crud fractions; dotted lines reference compounds. Reference compound
fractions and R f values identified in Table 3.
 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121 7

Fig. 2. IR transmission difference spectra of fractions of the initial plant organic phase supernatant to crud
S1-ai(8-13) and of matching fractions of reference compounds. Both crud and reference compounds were
separated by TLC on silica gel using heptanerdichloroethane eluant. Fractions dissolved from the TLC plate
into heptane. Key: solid lines crud fractions; dotted lines reference compounds. Reference compound
fractions and R f values identified in Table 3.

solution S1-ai was identified by comparison of its UV and IR spectra with those of
fraction 2 obtained from the TLC of DSAO DSAO-2.. See the third and fourth traces
from the bottoms of Figs. 1 and 2.
AAHO fractions capable of binding copper were characterized by a broad band with
an absorbance maximum near 320 nm as was salicylaldoxime., which moved to 350 nm
with a shoulder near 370 nm upon complexation with copper. Similarly, for HNAPO-2,
the bands at 220 and 250 moved to 240 and 260 nm, respectively upon complexation
with copper; for DSAO fractions 2, 3, and 4, bands at 220 and 260 moved to
approximately 235 and 270, respectively, upon complexation with copper. Both DSA
and HNAP had band maxima near 340 nm, as did salicylaldehyde and 2X-hydroxy-
acetophenone. Figs. 1 and 2 include spectra of the DSA-2 and HNAP-2 fractions, which
were the major components of those unoximated. reagents.
Although benzisoxazole and benzoxazole decomposition products of AAHO reagents
were expected, none were found by comparison with UVVisible or with IR spectra of
known compounds. These compounds will not be discussed further. Spectra of these
compounds will be presented in another paper for comparison with photolysis products
of AAHO reagents.
8 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121

2.8. IR spectra, TLC-mobile compounds

Additional confirmation of the identities of fractions obtained by TLC fractionation

of crud components and reagents was obtained by transmission IR analyses of the
fractions. Fig. 2 shows a typical set of spectra for the fractions and known compounds.
Table 1 identifies the major IR bands in the lower IR region, along with the molar
absorptivities determined for individual bands.
IR spectra of the OH stretching region were mostly uninformative, with the following
exceptions. Fraction DSAO-3 showed two types of phenolic OH. The sharpness of the
3600 cmy1 OH stretching band of AAHOs was characteristic of monomeric compounds
dissolved in non-hydrogen bonding solvents e.g., heptane.. Because monomers of
AAHO were already internally hydrogen bonded syn isomer., the band at 3600 cmy1
decreased in intensity, but did not shift upon dimerization. Broad bands near 3250 and
3450 cmy1 in the AAHO spectra were characteristic of dimer formation w21x; they
disappeared in the presence of copper or upon dilution.

Table 1
Characteristic IR absorptions and band strengths for reference compounds
Compound Characteristic absorptions, cmy1
DSA 1664 1623 1591
ea 766 mw b mw
HNAP 1649 1619 1590
e 423 33.8 48.4
p-NP 1753 1616 1595.6
e mw 19.5 w, sp
SX-7 1606
e 17.8
Nap-acid 1711
e 226
TXIB 1743.0
e 1096
HNAPO 1723 1637 1622 1582 1513 1495
e mw w 59.6 16.1 24.3 135
HNAPOCu 1639 1611 1541 1497
e 48.8 57.2 43.4 s
DSAO 1625 1584 1513 1497
e 98.8 mw sh 216
DSAOCu 1647 1612 1596 1543.0 1506
e 112 138 w 115.8 122
a
Molar absorptivity, 1 moly1 cmy1 .
b
Band strength abbreviations mentioned in the succeeding notes.
w, weak.
m, medium.
s, strong.
v, very.
sh, shoulder.
sp, sharp.
Table 2
IR characteristic absorptions of IOL and AOL from 12 cruds
Characteristic absorption, cmy1 strength.
Crud name Type Carboxylic esters Carboxylic acids Aldehyde Ketone
E1-a(2-19) AOL 1738-1711 wb. 1661.0 s. 1646.6 w. 1621.8 m. 1610.8 m. 1588.9 w. 1542.1 w. 1512.7 sh.
E1-ai(2-19) IOL 1743.6 wb. 1559.9 sh. 1646.0 m. 1621.2 m. 1609.7 s. 1542.1 m.
E1-a(4-30) AOL 1740 wb. 1710.7 wb. 1661.6 s. 1647.8 w. 1621.2 m. 1610.3 w. 1588.9 w. 1541.6 w. 1511.0 sh.

R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121

E1-ai(4-30) IOL 1661.6 sh. 1645.5 m. 1610.3 s. 1541.6 m.
E1-PD-a AOL 1745.3 m. 1714.1 w. 1661.0 s. 1647.2 w. 1621.2 m. 1610.3 m. 1591.8 sh. 1542.7 m.
E1-PD-ai IOL 1741.3 w. 1661.0 w. 1646 m. 1610.3 s. 1590.0 sh. 1542.1 m.
E1-a(8-13) AOL 1740.0 mb. 1710.0 mb. 1660.5 s. 1646.6 w. 1621.4 m. 1588.3 w. 1512.7 w.
E1-ai(8-13) IOL 1663.4 sh. 1646.0 m. 1610.3 s. 1541.6 m.
S1-a(8-13) AOL 1746.5 wb. 1711.0 mb. 1661.6 vs. 1647.8 s. 1616.6 m. 1590.6 m. 1512.7 w.
S1-ai(8-13) IOL 1709.5 w. 1661.6 w. 1646.6 w. 1621.2 w. 1609.7 m. 1588.3 w. 1541.6 w. 1512.1 sh.
E1-Mi-a AOL 1740.0 b. 1711.8 sh. 1661.0 vs. 1648.3 w. 1622.4 m. 1608.5 w. 1588.9 w. 1512.1 sh.
E1-Mi-ai IOL 1661.0 w. 1647.2 w. 1621.2 sh. 1609.1 s. 1590.6 sh. 1542.1 m.
S1-Mi-a AOL 1748.8 m. 1699.7 sh. 1661.6 vs. 1647.8 s. 1616.0 w. 1607.9 w. 1590.6 m. 1512.1 sh.
S1-Mi-ai IOL 1661.0 w. 1647.2 w. 1621.8 sh. 1609.1 s. 1587.7 sh. 1542.1 m.
E1-PV-a AOL 1748.2 vs. 1713.6 s. 1661.0 vs. 1647.8 m. 1621.8 w. 1607.9 w. 1591.8 w. 1512.1 sh.
E1-PV-ai IOL 1662.2 w. 1647.2 w. 1607.4 sh. 1590.0 sh. 1541.0 m.
S1-PV-a AOL 1748.2 m. 1711.3 m. 1661.6 vs. 1647.8 s. 1615.4 w. 1606.2 w. 1590.0 m. 1512.1 sh.
S1-PV-ai IOL 1662.2 w. 1647.2 w. 1606.2 m. 1590.0 sh.
So-E1-a AOL 1739.5 vs. 1713.0 vs. 1661.6 s. 1623.5 s. 1585.4 m. 1512.1 sh.
So-E1-ai IOL 1740.7 vs. 1719.3 sh. 1663.4 sh. 1647.2 m. 1611.4 m. 1542.7 m. 1504.6 w.
Te-E1-a AOL 1745.9 mb. 1711.8 mb. 1661.6 s. 1648.3 m. 1621.2 m. 1590.0 m. 1539.8 w.
Te-E1-ai IOL 1662.8 w. 1647.2 m. 1610.3 m. 1542.1 m.
Soc-E1-a AOL 1745.9 mb. 1712.4 mb. 1661.0 m. 1647.2 m. 1613.1 m. 1590.6 w. 1542.1 mw. 1512.1 sh.
Soc-E1-ai IOL 1661.0 w. 1647.2 m. 1610.8 s. 1542.7 m.

Note: pairs of samples taken from the same crud are separated by underlines.
-ai and IOL refer to Initial plant Organic Liquid solution, whereas -a and AOL refer to supernatant diluent solution after extraction of crud solids with acetone,
evaporation, and centrifugation Acetone-Off Liquid..
Refer to text for procedures.

9
10 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121

Fig. 3. IR transmission difference spectra of pairs of liquids obtained from USA cruds. Key: solid lines initial
organic supernatant phase ai.; dotted lines s AOL liquids separated diluent upon evaporation after
extraction of crud solids with acetone, a.. In one case, both the E- and S-stage cruds were analyzed.

Transmission IR spectra of the ultracentrifuged IOLs initial plant organic phases.

and the extracted AOL liquids acetone extracts from cruds. were compared for the 12
cruds listed in Table 2. The solutions were not subjected to TLC fractionation. Solutions
were analyzed undiluted, to allow comparison of the relative concentrations of car-
boxylic esters, carboxylic acids, and de-oximated reagents aldehydes and ketones..
Figs. 3 and 4 show IR spectra of pairs of liquids obtained from USA cruds, for the IOL
marked ai. and AOL liquids marked a.. In four cases, both the E- and S-stage
cruds were analyzed. Fig. 5 shows similar pairs of spectra from three cruds obtained
from Chile, along with spectra from another E-stage US sample.

2.9. Identification of indiidual reference compounds

TLC fractions were numbered for reference; the least mobile fraction lowest R f .
was number 0. Many number 0 fractions did not move on the TLC plate when 1:1
heptanerDCE was used for elution. Table 3 lists the fraction numbers and R f values
obtained with 1:1 heptanerDCE. The spectral characterization of the fractions obtained
in preparative scale TLC is described here for several reference compounds.
Similar to the findings of Ritcey and Wong w19x, IR bands for carboxylic acids and
esters. were absent from both the IOL and AOL organic solutions isolated from both E
 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121 11

Fig. 4. IR transmission difference spectra of pairs of liquids obtained from USA cruds. Key: see Fig. 3. In
these cases, both the E- and S-stage cruds were analyzed.

and S cruds. These bands were, however, present in the fractions found to be TLC
immobile when eluting with heptanerDCE.

2.9.1. p-NP
One band appeared in TLC R f s 0.33. with characteristic absorptions at 1615.6
cmy1 in the IR and at 220 nm E 2-band. and 275 nm B-band. in the UV region.

2.9.2. DSA
The major component DS-2, R f s 0.68. had characteristic absorptions at 1664.4
cmy1 in the IR region and at 342 nm weak n p ) band, R-band. and 230 nm
intense K-band. in the UV region w22x. Fraction DS-1 R f s 0.33. had not only the
same R f as p-NP, but also similar UV and IR spectra. Fraction DS-3 R f s 0.78. had
similar spectra to DS-2.

2.9.3. HNAP
The major component R f s 0.58. had characteristic absorptions at 1648.7 cmy1 in
the IR and at 342 nm weak n p ) band, R-band. and 250 nm intense K-band. in the
UV. The other component R f s 0.33. had similar spectra to p-NP, which was one of
raw materials of HNAP.
12 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121

Fig. 5. IR transmission difference spectra of pairs of liquids obtained from three Chilean E-stage cruds and
one USA E-stage crud. Key: see Fig. 3.

2.9.4. SX-7
The diluent had no strongly retained fractions observable in TLC. Treatment with
silica gel to concentrate polar components did allow isolation of carboxylic compounds
vide infra.. Two fractions almost moved along with solvent. The fraction with

Table 3
Thin layer chromatographic R f values, and fraction numbers for reference compounds
Compound
DSA 0.33 1. 0.68 2. 0.78 3.
HNAP 0.33 1. 0.58 2.
p-NP 0.33
SX-7 0.87 1. 0.94 2.
Nap-acid 0. ) 0.90
HNAPO 0. 0.18 2. 0.31 3. 0.54 4.
HNAPOCu 0. 0.27 2. 0.59 3.
DSAO 0. 0.25 2. 0.36 3. 0.64 4.
DSAOCu 0. 0.32 2. 0.74 3. 0.85 4.

Notes: Compound abbreviations in Section 2.

0. s has immobile fraction at origin.
a. s fraction number.
 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121 13

R f s 0.87 SX7-1. appeared dark under UV light. The fraction with R f s 0.94 SX7-2.
did not quench fluorescence, but became yellow after exposed in air for several hours.

2.9.5. HNAPO
In addition to the major component HNAPO-2, R f s 0.18. and a trace amount
staying in the starting position HNAPO-1, R f s 0., the other two fractions HNAPO-3,
R f s 0.31 and HNAPO-4, R f s 0.54. were identified as p-NP and HNAP, respectively
by IR, UV, and R f value. The major component oxime. had a weak R-band at 316 nm
UV region. and a medium strength n C 5 N absorption at 1621.8 cmy1 IR region..

2.9.6. DSAO
In addition to the major component DSAO-2, R f s 0.25. and a trace amount staying
in starting position DSAO-1, R f s 0., the other two fractions DSAO-3, R f s 0.36 and
DSAO-4, R f s 0.64. had similar UV spectra to the major component. The IR spectra of
Fractions a3 and a4 were similar to each other but quite different from true DSAO.
Fractions a3 and a4 in heptane solution were able to extract copper at pH 4.1; they
were most likely ring substitution isomers or synanti isomers, and may be chain-length
analogues of each other. The major component DSAO oxime. had a weak R-band at
316 nm UV region. and a medium strength n C 5 N absorption at 1625.3 cmy1 .

3. Results and discussion

This discussion pertains to the components of crud which are soluble in the SX-7
diluent and which are mobile in TLC using low-polarity heptanerDCE solvent. The
majority of the liquid obtained by acetone extraction of crud solids AOL. is merely
diluent. A detailed description of the separation of the organic fractions which were
TLC-immobile using heptanerDCE will be presented in a separate paper. A brief
discussion of what is now known about the immobile compounds follows a description
of the TLC-mobile fractions.
Normal centrifugation, such as is commonly available in commercial SX plants, can
serve to partly separate phases w18x. More extreme g-fields are required for adequate
separation, however, because even benchtop laboratory centrifuges fail to separate crud
into its constituent components for chemical analysis.
Ultracentrifugation 10,000 rpm. was successfully applied to copper-SX cruds from
both extraction and strip stages. The primary separation by ultracentrifugation resulted in
compact solid fractions having low water and diluent content and in liquid fractions free
of solids. The resulting fractions were subjected to chromatographic separation tech-
niques and those secondary fractions were subjected to spectrochemical analyses. The
TLC method is, to some extent, a reasonable model for the affinity of certain organic
compounds for the hydrophilic silicate solids found in massive cruds.
In this laboratory, samples of SX crud from several different Arizona copperrAAHO
circuits were completely stable no breakage of emulsion or precipitation of particles.
for over 5 years in capped glass bottles. The organic supernatants from these samples
were analyzed and found to contain no remaining oxime function, and no residual
14 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121

copper loading capacity. This leads to a partial conclusion: the AAHO reagents are not
themselves responsible for the stability.

3.1. Separation and identification of four cruds

Two cruds, strip-stage S1-a(8-13) and extraction-stage E1-a(2-16), were separated

and analyzed. After ultracentrifugation, the supernatant IOLs initial plant organic
liquids. from these cruds were called S1ai and E1ai. After acetone extraction and
evaporation, the brown dark organic solutions acetone-off liquid or AOL. were called
AOL S1a and AOL E1a.

3.1.1. S1ai
An IOL. Eight of the fractions of S1ai from TLC matched HNAPO-2, DSAO-2,
p-NP, HNAP, DSA-2, DSA-3, SX7-1 and SX7-2 by R f , IR, and UV spectra Fig. 1..
The remaining fraction S1ai-1. stayed at the starting position, had a band near 1745
cmy1 , and had a brown color, but was not identified. Fraction S1ai-1 had a strong
absorption near 200 nm in the UV and broad absorption around 17101740 cmy1 in IR
spectrum aliphatic carboxylic acidrester region.. The copper complexes decomposed as
they moved on the plate, resulting in a dark streak on the plate; spectral matching of
those fractions with the reference materials were not very precise.

3.1.2. S1a
An AOL. Five fractions of S1a from TLC matched p-NP, HNAP, DSA-2, DSA-3,
SX7-1 by R f , IR, and UV spectra. An additional one stayed at the starting position, had
a band at 1705 cmy1 , and had a brown color, but was not identified. Fraction a2 was
only tentatively identified as p-NP, because it exhibited an additional band near 1748
cmy1 possible oxidation product of p-NP.. No streaking due to copper complex
decomposition was observed. It followed that the crud formed in the stripping section
contained the degradation products or raw materials. of HNAPO and DSAO but neither
the extractants nor the copper complexes.

3.1.3. E1ai
IOL. Nine fractions were found in TLC of E1ai. One of them stayed at the starting
position and was not identified. The other eight fractions were identified as HNAPO-2,
p-NP, HNAP, DSA-2, DSAO-Cu, SX7-1, and SX7-2 by R f , IR, and UV spectra.
Streaking due to copper complex decomposition was observed.

3.1.4. E1a
AOL. Seven fractions of E1a from TLC matched HNAPO-2, DSAO-2, p-NP,
HNAP, DSA-2, SX7-1 and SX7-2 by R f , IR, and UV spectra. One fraction stayed at the
starting position and was not identified. No streaking due to copper complex decomposi-
tion was observed. It followed that the crud formed in the extraction section contained
extractants and their degradation products or raw materials. but not the copper complex.
 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121 15

Fig. 6. IR spectra of solids in KBr pellets. Known kaolinite and illite minerals, the sum of their spectra, and
the inorganic solid obtained from crud E1-a(4-30).

3.1.5. Insoluble materials

The AOS organics all had bands near 1720 cmy1 indicating aliphatic carboxylic acid
functions, in the 34003500 cmy1 , 1630 cmy1 , and 1050 cmy1 regions indicating
alcohol functions. Colloidal silica also has bands in those regions, which may have
suggested the presence of silica to other investigators. Fig. 6 shows the KBr pellet IR
spectra of one of the acetone washed, inorganic crud solids from which the organics
have been removed E1-a(4-30).; spectra of standard samples of kaolinite and illite
minerals, and the sum of those spectra, for comparison with the crud spectrum. The
inorganic solids had sharp bands at 3697, 3669, 3652, and 3620 cmy1 which are
characteristic of kaolinite clay w23x, in addition to more broad bands due to OH groups in
the minerals. Both illite and inorganic crud solids exhibited a broad, weak band below
1700 cmy1 OH bending..

3.2. IR analyses of soluble organic components from 12 cruds

The centrifugationracetone extraction methods were applied to 12 different cruds,

including the S1-a(8-13) and E1-a(2-19) described earlier, and three cruds from Chile.
In sample So-E1-a, TXIB a symmetric branched-chain dicarboxylic diester. was used
as a modifier. TLC analysis was not applied to these samples. The objective was to
16 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121

provide a measure of the relative concentrations of identifiable diluent-soluble compo-

nents in cruds and in the respective initial plant organic phases.

3.2.1. Segregation mechanism

Separation of phases leads to a marked decrease in interfacial area, both between
particles and solution and between solutions. The loss of interfacial area can cause
surface active compounds to become saturated on the remaining surfaces and to
redissolve in the solutions. This may account for the increased concentrations of certain
compounds in the AOL phase upon evaporation of acetone from the solids extract; solid
particles had been removed and the remaining organic mass had little surface area. The
relatively large volume of AOL obtained during acetone evaporation indicated that
ultracentrifugation did not reduce interfacial areas as markedly as did the acetone
extraction process.
It is possible that real crud contains aliphatic acids and esters because they form a
viscous phase of low solubility driven by precipitation. which adheres to surface active
compounds adsorbed onto the kaolinite and other inorganic solids. This type of phase
separation could account for the higher concentration of DSA and HNAP, for example,
in the cruds than in the free organic phase. The waxyrgummy nature of the AOS
material precipitated during evaporation of acetone extract. is an indication of its
chemical inhomogeneity.
These results do not indicate whether the dominant mechanism of crud formation
occurs in free diluent solution, in the separated diluent-insoluble organic phase, or at the
interfaces between any assorted immiscible phases. It is unlikely, however, that acid
catalyzed hydrolysis can occur within the separated insoluble-organic phase, because
ionized acids will be excluded low dielectric constant.. Hydrolysis is similarly unlikely
to occur at the surfaces of inorganic particles after they have been coated with
precipitated organic material. Hydrolysis is most likely to occur at aqueous
phaserorganic phase interfaces. Reactions other than hydrolysis must be considered,
however, because the majority of the crud mass is not composed of hydrolysis products
of the AAHO reagents.

3.2.2. Results
Four features, discussed here, were found for all cruds when comparing the relative
amplitudes of IR bands between the supernatant initial organic IOL. phases and the
respective diluent-soluble organic components isolated by acetone extraction AOL..
The solvent was essentially identical with SX-7 in both the US and Chilean cases. Table
2 lists some of the IR bands obtained from these cruds and Figs. 35 show comparisons
between spectra of the IOL and AOL phases.

3.2.2.1. What is the relatie copper complex content of cruds?. In every case, IR bands
for the AAHO reagents were observable in the AOL phase and nearly absent in the IOL
phase, because the reagent is mostly complexed with copper ions even after the strip
stage. When these bands were taken into account, the bands due to copper complexes
were shown to be comparable or smaller in AOL than in IOL phases. In samples
 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121 17

So-E1-a and Te-E1-a, the copper complexes were nearly absent from the AOL. We may
conclude that the copper AAHO complexes are not retained in or on the solid or waxy
portions of cruds.

3.2.2.2. What is the contribution of de-oximated reagents to crud?. Because the molar
absorptivities of DSA and HNAP were about 7.5 times larger than for DSAO and
HNAPO, respectively, the concentrations of DSA and HNAP relative to the oximated
reagents, ranged from essentially nil in IOLs to near 50 mol% in AOLs. Samples
S1-Mi-a and S1-PV-a, particularly, contained much larger DSA and HNAP concentra-
tions in the AOL than did any of the other US crud samples, but about the same as in the
Chilean samples. We conclude, therefore, that DSA and HNAP are retained either on the
inorganic crud solids or in the waxy organic crud solids, to a greater extent than are the
respective oximes or copper complexes. Hydrolysis is acid catalyzed, and the strip stage
is much more acidic than the extraction stage, making the strip stage the probable source
of hydrolysis products. These compounds are quite soluble in diluent, however, so they
are also present in extraction stage IOL.

3.2.2.3. Are extraction and strip cruds different?. Strip cruds contained more DSA and
HNAP, relative to the DSAO and HNAPO, than did the respective E cruds in all of the
E r S extraction stage crudrstrip stage crud. sample pairs examined. This was particu-
larly obvious in the E1-a(8-13) vs. S1-a(8-13) comparison. Because the plant organic
phase is pumped from the S stage back to the E stage at an enormous rate relative to the
rate of hydrolysis, the S and E stage plant organic phases have essentially the same
concentrations of hydrolysis products. The higher concentration of hydrolysis products
in the S stage crud must, therefore, have been due to stronger distribution into S stage
crud than into the E stage crud. That difference suggests that there were additional
differences between the cruds from the two stages.

3.2.2.4. What other compounds are present in cruds?. AOL solutions from cruds
contained larger proportions of carboxylic compounds i.e., they exhibited IR bands at
1710 cmy1 aliphatic carboxylic acids. and at 1740 cmy1 aliphatic carboxylic acid
esters., than did the respective initial plant organic solutions. In the E r S extraction
stage crudrstrip stage crud. sample pairs examined, the E cruds had larger bands for
these acids and esters than the respective S cruds, by factors of four or more. This may
be the key to the differential distribution of hydrolysis products discussed above.
In the So-E1 samples, the 1740 cmy1 region was obscured by bands from TXIB a
diester., but aliphatic carboxylic acids could be distinguished and were present in the
AOL at concentrations five times as high as in any other sample. TXIB was only slightly
more concentrated in AOL than in IOL. This material may have been liberated from the
crud by desorption as the interfacial area became smaller. These observations do not
mean that the carboxylics are generated in the extraction stagethey only become
concentrated there. Recirculation of the plant organic phase allows transport between the
extraction and strip stages.
As mentioned previously, the IR bands showed that the E cruds retained extractants
and other organics, but not the AAHOCu complexes.
18 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121

The previous observations concerning aliphatic carboxylic acids and esters in AOS
solids precipitated during acetone extraction of crud. and in the So-E1 cruds are
consistent with another partial conclusion about copper-SX cruds. The majority of crud
solid is partially oxidized, insoluble organic matter.

3.3. Reconstitution of crud from crud components

Some additional observations were made on the insoluble organic crud solids which
precipitated during acetone evaporation of the extracts acetone-off solids or AOS..
These same compounds were observed to be immobile during TLC using heptanerDCE
as eluant.
Attempts were made to form crud by mixing initial plant organic phases IOLs. with
either aqueous pregnant leach solutions from heap-leaching. or strip solutions in the
presence and absence of particulate additives. Crud could not be formed using clean
powdered silica gel, alumina, kaolinite, illite, or actual cleaned crud inorganic solids. In
each case, the inorganic powder settled to the bottom, in essentially quantitative yield.
Crud could, however, be reconstituted with methanol and acetone extracts of the low
solubility organics, in the absence of inorganic particulates. AOS from sample E1-a(8-13)
was redissolved in methanol or acetone it was less soluble in methanol.. One drop was
layered by pipet at the interface between 20 ml aqueous and 20 ml organic supernatant
phases. A filmy precipitate formed instantly at the interface, which recollected at the
interface even after vigorous shaking. When any of the above inorganic powders was
subsequently added to the vial, this small amount of insoluble organic material retained
a visible amount of inorganic powder. Phase disengagement became much slower,
indicating that the combined organicrinorganic films was more rigid that the organic
film alone.
From these tests we conclude that the relatively insoluble compounds are necessary
for crud formation, and that particulates may not be. Particulates may only provide a
coagulation site for the precipitation of organics. Crud formation was apparent to the eye
without agitation. An additional conclusion, then is that the particular agitation in a
given system only has an effect on the physical distribution of crud films, massive,
gelatinous, etc..; in the presence of these insoluble organic components, crud will form
with any type of agitation.

3.4. Additional issues

3.4.1. Adsorption on crud solids

Another measure of the attraction of certain of the organics present in copper-SX
systems for the kaolinite solids was found by using cleaned inorganic solids from real
crud as an adsorbent. The tan colored inorganic solid obtained from crud S1(4-30) after
alternating acetone extraction and ultracentrifugation contained an identifiable portion of
the mineral kaolinite. Separately, IOL phases S-1a(4-30) and E-1a(4-30) were stirred
with the cleaned inorganic crud solids for 1 h and the mixtures ultracentrifuged.
Organics adsorbed to the solids were isolated by acetone extraction and evaporation and
IR spectra were obtained of the organic solutions. The presence of a strong, sharp band
 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121 19

at 1738 cmy1 showed that the cleaned crud solid had adsorbed additional aliphatic esters
from the organic phase. The inorganic crud solid itself exhibited only a broad, weak
band below 1700 cmy1 OH bending, Fig. 6..
Whether collection of organics on the silicate solids was initially by surfactant-like
adsorption or by simple precipitation is unknown. Because crud cannot be completely
removed from a circuit once formed, however, the initial mechanism may be unimpor-
tant except in new circuits.

3.4.2. SX system components

Very small amounts of carboxylic acids in fresh SX-7 diluent could be removed by
adsorption onto clean silica gel. The carboxylic acid functions were identified in IR
difference spectra between the treated and untreated SX-7 from a band at 1720 cmy1 .
By TLC, two fractions have been separated Table 3.. The slower moving
componentstill fast on this scalehad a strong IR band near 1606 cmy1 . Naphthenic
acid could not be detected in the SX-7 by TLC; neither the TLC mobility nor the
UVVisible spectra corresponded to either of the observed fractions of SX-7.
The carboxylic acids in crud may or may not have actually come from the diluent, or
from AAHO degradation, but over time such materials could accumulate in crud. For
that reason, even minor sources are important.

3.4.3. Exposure to UV-light

Results to be described elsewhere indicated that exposure to UV-light produced
polymers of AAHO. If the polymers are coupled through the AAHO alkyl chains,
neither the IR spectra of the hydroxyoxime functions nor the UVVisible spectra would
detect the change. This could explain why it has been difficult to observe new bands
indicative of collected degradation products in cruds: the polymers and monomeric
AAHOs would have nearly identical spectra. In the sections on analyses of unseparated
crud organics here, the bands attributed to DSA and HNAP may actually be partially
composed of contributions from these polymers. This aspect will need a great deal of
attention.

4. Conclusions

As first steps toward an ultimate solution to the crud problem, three approaches are
being used to understand what compounds or physical characteristics are associated with
crud and crud upsets. In this paper, we have explored the first of two of the following
three steps: 1. Analyze all materials added to SX circuits to establish a database for
identification of compounds separated from cruds; 2. Examine as many cruds as
possible to establish a correlation between organic phase andror crud composition and
crud episodes or crud runs. A comparison of the organic contents of cruds from
different mines and SX stages was begun 12 different cruds, to date.. Patterns of where
certain insoluble compounds and degradation products collect in the SX circuits have
become apparent; 3. Examine models of known mechanisms for the degradation of SX
20 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121

circuit reagents and solvent, in attempts to establish potential sources for the compounds
discovered in cruds.
Some general conclusions may be drawn from the results of Steps 1 and 2 on the
analyses of copper-SX cruds: 1. Cruds contained larger proportions of DSA and HNAP
than in the supernatant organic phase; 2. The strip stage cruds contained more of the
hydrolyzed, de-oximated DSA and HNAP, relative to the oximes DSAO and HNAPO,
than did the respective extraction stage cruds; 3. Cruds contained larger proportions of
carboxylic compounds, including aliphatic carboxylic acids and aliphatic carboxylic acid
esters, than did the respective supernatant organic solutions; 4. Extraction stage cruds
contained more diluent-soluble carboxylic acids and esters that did the corresponding
strip stage cruds; 5. The diluent-insoluble organic components of crud contain large
quantities of carboxylic acids and esters; 6. Copper complexes of AAHO reagents are
not concentrated in the crud. Recirculation of the plant organic phase ensures that the
concentrations of hydrolysis products and carboxylic acidsresters in the strip stages are
essentially to those in the extraction stage. Although acid hydrolysis must be faster in
the strip stage, the increased hydrolysis product concentrations in strip stage cruds may
be linked to the decreased concentrations of carboxylic acids and esters in the strip stage
cruds.
We have adopted the hypothesis, subject to revision, that low-polarity compounds
which are soluble in typical copper-SX circuit diluents are less likely to cause crud
episodes, or even to be accumulated in crud, than are either the more polar or the less
soluble compounds. The polarity is reflected in TLC behavior. Lower mobility on silica
gel TLC plates is an indication of greater polarity, but highly insoluble non-polar
compounds are also immobile. Extremely polar compounds are swept out in the raffinate
and not accumulated in crud. The low-mobility TLC fractions did contain carboxylic
functions.
More specific conclusions may be drawn concerning the role of insoluble organics in
crud. These compounds comprise the majority of the solid mass of crud in the
copper-SX circuits examined. The addition of insoluble organic compounds caused
reconstitution of crud from decanted organic and aqueous phases. These compounds
were required for reconstitution of crud, whereas inorganic particulates were not.
Inorganic particulates were incorporated into the interfacial mass formed by the insolu-
ble compounds, but did not reconstitute crud in the absence of the insoluble compounds.
These observations do not mean that the carboxylic acids and esters are generated in
the extraction stage. SX circuits rapidly reach a dynamic equilibrium due to recircula-
tion. Similarly, the observation that the de-oximated products of AAHO degradation are
concentrated in crud does not mean that they cause crud. The de-oximation products
merely have slightly enhanced distribution from diluent solution into the highly viscous
organic mass residing in crud.
In the following paper w24x, we describe results from modeling the mechanisms for
generation of the compounds discovered in cruds. Three mechanisms: a. exposure to
UV-light, b. contact with concentrated H 2 SO4 , and c. oxidation of the organic phases,
produced polar, low solubility compounds. UV light appears to create polymeric
materials from the AAHOs. These polymers adsorb strongly to silica and have low
solubility in hydrocarbon solvents. As the insoluble components of crud are separated
 R.P. Sperline et al.r Hydrometallurgy 50 (1998) 121 21

and identified, further clues to the sources. of crud components will emerge. This
chemical detective approach should lead to practical methods for crud abatement and
control.

Acknowledgements

We thank the Minerals Industry Division, Henkel for a grant in support of this
research.

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