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REVIEW OF OIL SHALE RESEARCH IN AUSTRALIA
Peter G. Alfredson
Division of Energy ChemistryCommonwealth Scientific and Industrial Research Organization
Private Mail Bag 7
Sutherland, NSW 2232
AUSTRALIA
ABSTRACT
In the last five years, there has been a major
increase in oil shale research in Australia in
parallel with economic feasibility studies of the
exploitation of the major Julia Creek, Rundle and
Condor deposits. The results of these studies and
the status of research being carried out primarily
in government and university research laboratories
are summarised. The scope of this research includes
geology, petrology and geochemistry of oil shales,
retorting chemistry and kinetics, upgrading of shale
oils and environmental studies.
INTRODUCTION
The oil shocks of the 1970s generated an
immediate and urgent worldwide interest in
synfuels. In the Australian context, this interest
was a result of diminishing indigenous petroleum
resources with a corresponding anticipated decline
in production by the late 1980s, a desire to reduce
the level of petroleum imports in view of their
increasing cost, concern about the security of
supplies from the Middle East, and the perception
that the cost of synfuels was not much more than
world oil prices.
There have been significant changes in some of
these factors in the last two years, e.g. the fall
in world oil prices and the easing of supply,
discoveries of new Australian oil and gas fields
(both on-and off-shore), and significant increases
in the estimated production costs for synfuels,
which have reduced the apparent urgency for synfuels
production. However, Australian self-sufficiency in
oil is still estimated to fall from a peak of more
than 85 per cent in the mid-1980s to under 60 per
cent in the year 2000(1). Meanwhile the timescale
for development of a major synfuels industry remains
of the order of 10 to 20 years.
Oil from shale is one of the attractive options
for the production of synfuels in view of the large
Australian resources. Economic feasibility studies
of the exploitation of the major Julia Creek, Condor
and Rundle deposits have been carried out in the
last five years and there has been a significant
parallel expansion of oil shale research.
The scope of this research is outlined in
the Australian Department of Resources and
Energy's "Compendium of Australian Energy
Research, Development and Demonstration Projects
No. 5, June1984"
(2) and the papers presented at
the First and Second Australian Workshops on Oil
Shale held, respectively, in 1983 and 1984(3,4).
This paper briefly describes Australia's oil
shale resources and the results of the
feasibility studies, and reviews the status of
oil shale research in Australia.
OIL SHALE RESOURCES
Oil was produced from oil shale in
Australia for most of the period from 1865 to
1952 and these early operations have been
described previously(5,6) . They were based on
high grade torbanite in New South Wales and
tasmanite in Tasmania, but the remaining
quantities of these very high grade (up to
800 L t-l) materials are so small that they are
of no significance for a future large-scale
Australian synfuels industry.
Australia's major oil shale resources (Table
1) are located in Queensland (Figure 1) with in
situ shale oil resources exceeding 7 x10^
m3.
TABLE 1. AUSTRALIAN OIL SHALE RESOURCES
Deposit In-situ Shale Av arage Reference
Oi 1 Resources Oil Yield
(IO6m3) L
fl
Condor 1500 66
Duaringa 600 82
Nagoorin 400 91
Lowmead 120 84 > (7)
Rundle 400 100
Stuart 400 94
Yaamba 450 95
Julia Creek 3200 70 (8)
All of these deposits are of Tertiary age except
for the Cretaceous Julia Creek deposit(9).
The Julia Creek deposit is part of the
extensive Toolebuc Formation which stretches
from the Gulf of Carpentaria through the
0271-0315/85/0018-0162 $00.20 162 1985 Colorado School of Mines
Townsville
Proserpine
YAAMBAA
DUARINGAA JkRUNDLE
STUART^%GiQdstone
NAGOORINA^s
LOWMEAD
FIGURE 1. QUEENSLAND OIL SHALE DEPOSITS
south-western corner of Queensland into northern New
South Wales and South Australia. It consists
predominantly of black carbonaceous and bituminous
shale and siltstone with limestone lenses and
coquinites, and has an average total thickness of
22 m including 7 m of oil shale. The Julia Creek
deposit lies within 20 m of the surface and is
therefore amenable to open pit mining. The oil
shale is considered to have formed in a relatively
restricted marine basin.
By contrast, the Tertiary deposits formed in a
fresh-water lacustrine environment. There are two
main oil shale types -
a normal brown oil shale
and a black carbonaceous oil shale whose
properties are comparable with those of a brown
coal. The Tertiary deposits comprise exceedingly
thick sedimentary sequences (up to 1000 m) and
are also amenable to open pit mining.
Typical properties of these oil shales are
summarised in Table 2. By comparison with Green
River shale, the Queensland oil shales are much
more variable, generally give a lower oil yield
(factor of 2), have a higher moisture content
(factor of 10) and, except for Julia Creek, are
not associated with carbonate minerals. Because
of these differences, processes and technology
developed for Green River shale cannot simply be
transferred to Queensland shales without further
research, development and demonstration.
ECONOMIC FEASIBILITY STUDIES
Economic feasibility studies have been
carried out on the exploitation of the Julia
Creek(lO), Rundle(ll) and Condor (12) deposits
and the published results are compared in
Table 3. Dravo, Superior, Lurgi and Tosco
technologies were generally considered in these
studies. A pre-feasibility study of the mining
and infrastructure requirements for the Yaamba
deposit has also been reported( 13) .
The Rundle and Condor studies were under
taken as joint ventures between Southern Pacific
Petroleum NL/Central Pacific Minerals NL
(SPP/CPM) and Esso Exploration and Production
Australia Inc. and Japan Australia Oil Shale
Corporation (JAOSCO), respectively, and completed
in 1984. The Rundle study (with Esso as
operator) was part of a work program, costing
more than A$32 million during 1981-84, which
involved investigations of mine planning, shale
Deposit
TABLE 2 - TYPICAL CHARACTERISTICS OF SOME AUSTRALIAN OIL SHALES
Average Dominant
Oil Yield, Kerogen
L t"1 Type
Dominant Moisture, H/C Ratio
Mineralogy wt % wet of Kerogen
basis
Condor 66 I Clay/quartz 8 1.4
Duaringa 82 I Clay 32 1.5
Nagoorin 91 III, I Clay 26 1.1
Julia Creek 70 II, III Calcite/silica 5 1.4
Lowmead 84 I, III Clay 23 n.a
Rundle 100 I Clay 20 1.6
Stuart 94 I Clay 19 1.6
Yaamba 95 I, III n.a. 28 n.a
163
TABLE 3. SUMMARY OF COST ESTIMATES FROM FEASIBILITY
STUDIES
RundleJulia
Creek Stage I Stages
I - III
Condor
Oil shale
throughput
tonnes /day 240 000 25 000 125 000 200 000
Shale oil
production,
barrels/day 100 000 15 800 81 800 82 100
Average oper
ating cost $15.16* n.a. n.a. 20
US$/barrel
Investment 5 750* 645 2650 2300
cost,US$106
Cost reference 1980 mid-1983 mid-1983 mid-1983
year
Reference (10) (11) (11) (12)
* Costs in $A
retorting, product upgrading, infrastructure and
environment. Pilot plant testing of Rundle oil
shale was carried out in the United States, The
Federal Republic of Germany and Sweden(ll). Esso
and SPP/CPM have recently announced agreement( 14) on
a continuation of the Rundle project as a joint
venture with Esso funding further development up to
a maximum period of 10 years.
The Condor study was carried out during 1982-84
by an engineering team staffed equally by Japanese
and Australian participants, supported by
independent international contractors, within a
total budget of US$24 million funded by JAOSCO.
JAOSCO shareholders comprise the Japan National Oil
Shale Corporation and 40 major Japanese companies.
The results of the study indicate that a development
of the Condor oil shale deposit would be feasible
under the assumptions incorporated in the study(12).
Discussions between SPP/CPM and JAOSCO are
continuing. A bulk sample of Condor oil shale was
excavated and shipped to Japan in late 1984 for
pilot plant retorting studies by the Japan Oil Shale
Engineering Co. A total of 82 000 tonnes of
overburden was removed, 39 000 tonnes of fresh oil
shale was mined, crushed and screened to produce
20 000 tonnes of product of the required size(15).
The earlier CSR Ltd study of the Julia Creek
project, which was finalised in 1980, assumed Tosco
technology, with raw shale also burned to provide
process fuel for retorting( 10) . An improved
retorting technology( 16,17) is under development
which involves fluidized bed combustion of spent
shale to provide process fuel and project power,
recycle of hot shale ash as a heat transfer
medium, with combustion and retorting carried
out under conditions in which the high calcite
content of the shale feed is used to eliminate
environmental and waste disposal problems.
Spent shale combustion is carried out at about
900C to allow the ash recirculation rate to be
as low as possible (1-1.5 times the raw shale
feedrate), and to decompose calcite which then
stabilises silica in the combustor in the form
of calcium silicate. Other important features
of the process are the exothermic reactions
which take place inside the mixer/retort and
allow cold raw shale to be fed to the process.
They include the reaction of sulphur compounds,
carbon dioxide and water vapour from retorting
with free lime in the shale ash, which makes the
production of hydrogen for shale oil upgrading
from the retort gas easier and cheaper. A l\
year study to test some of the features of this
new process in a 0.2-0.5 t d~l pilot plant in
Sydney has commenced ( 18) .
The Julia Creek and Condor studies
indicated that capital costs are divided
approximately equally between mining, retorting,
shale oil upgrading and the rest (including
infrastructure and environment). The major
operating costs are associated with the same
components, the mining costs being somewhat
higher. Although improvements in oil yields
from retorting may have the greatest impact,
since they also reduce mining requirements,
research into improved technology and processes
for mining, beneficiation of the oil shale fed
to retorts, shale oil upgrading, and the
resolution of environmental problems at accept
able costs all warrant serious consideration.
The importance of environmental studies for
those deposits close to the Queensland coast and
the Great Barrier Reef (Condor, Rundle, Stuart)
cannot be under-stated.
OIL SHALE RESEARCH PROJECTS
Table 4 summarises the scope of oil shale
research in Australia which has been published
or is in the public domain. It is not complete
for industrial research, e.g. involving the
164
TABLE 4. SUMMARY OF OIL SHALE RESEARCH IN AUSTRALIA
Organisations Involved
Topic
Tertiary CSIRO Divisions Industry and
Institutions Others
Characterisation -
geology, petro ANU, JCU, Me lb, EC, FF, M, ME BMR, CSR, MRL,
graphy, chemistry, physics New,
Qld,
NSW, QIT,
Woll
QLD, SPP/CPM
Beneficiation, on-line analysis Qld MP ACIRL, Esso,SPP/CPM
Chemistry of retorting (pyrolysis Qld, Tas, WAIT, EC, FF, MC, ME AMDEL, CSR,
mechanisms, kinetics and Woll Esso, MRL,
thermochemistry), combustion and SPP/CPM
gasification of spent shale.
Retorting processes, technology, Mon, Qld EC, ME CSR, SPP/CPM
flowsheets, economics
Upgrading of shale oils-
character NSW, Mac, Woll EC, ET, MS BHP, CSR,
isation, hydrotreatment, testing Esso
Environmental studies -
leachates, Qld, Woll EC, FF, GWR CSR, Esso
retort waters, waste treatment,
revegetation
Tertiary Institutions*: ANU = Australian National, JCU = James Cook, Mac =
Macquarie, Melb =
Melbourne, Mon = Monash, New =
Newcastle, NSW = New South Wales, Qld = Queensland, QIT = Queensland
Institute of Technology, WAIT = West Australian Institute of Technology, Woll = Wollongong.
(* Universities unless otherwise stated)
CSIRO Divisions: EC =
Energy Chemistry, ET =
Energy Technology, FF = Fossil Fuels, GWR = Groundwater
Research, M = Mineralogy, MC = Mineral Chemistry, ME = Mineral Engineering, MP = Mineral Physics, MS
= Materials Science.
Industry and Others: ACIRL = Australian Coal Industry Research Laboratories Ltd; Amdel = Australian
Mineral Development Laboratories Ltd., BHP = Broken Hill Proprietary Co. Ltd, BMR = Bureau of Mineral
Resources, Geology & Geophysics, CSR = CSR Ltd., Esso= Esso Australia Ltd, MRL = Materials Research
Laboratories, Department of Defence, QMD = Queensland Mines Dept, SPP/CPM = Southern Pacific Petroleum
NL/Central Pacific Minerals NL.
evaluation of large (up to hundreds of tonnes)
batches of oil shale in overseas pilot plants and
the industrial development of new retorting
technologies by Exxon Research and Engineering Co
(based on Rundle shale) or by the Japan Oil Shale
Engineering Co Ltd (Condor shale).
Funding for oil shale research comes from three
sources. The Australian Government's National
Energy Research Development and Demonstration
Program (NERDDP) committed A$1.9 x IO6 to oil shale
research from 1978 to 1984, compared with a total of
A$25.8 x 106 for synthetic fuels research. The
production of liquid fuels from shale currently
ranks as a medium priority for 1985 NERDDP
applications. In addition, industrial companies
have funded research with universities and CSIRO at
a cost exceeding A$1.5 x IO6. By far the largest
financial support for oil shale research is
represented by the Australian Government funding of
universities and CSIRO and is probably in excess
of A$4 xIO6 per year(19).
Most Australian oil shale research has
concentrated on laboratory studies of the
characteristics of oil shale materials and the
chemistry of retorting. The largest scale of
research is carried out in process development
units (typically 5-30 kg h~l). In the remainder
of this paper, it is not possible to provide a
detailed account of all the oil shale research
in Australia, but some of the principal
activities are reviewed.
GEOLOGY, PETROLOGY AND GEOCHEMISTRY
Exploration of the major oil shale deposits
in Queensland has revealed a complex sequence of
stratigraphic units and oil shale seams
corresponding to different sedimentary environ
ments. 0zimic(20) described the depositional
environment of the Toolebuc Formation,
165
Green et al.(21) defined the three main
stratigraphic units of the Condor deposit, Lindner
and Dixon(22) described the major oil shale and
clays tone units in the Rundle deposit and Ivanac(23)
summarised the geology of the Stuart, Nagoorin,
Lowmead and Duaringa deposits.
In association with the mining of a slot cut
within the Ramsay Crossing Member of the Rundle
deposit to obtain 10 000 m3
of oil shale for process
testing, Coshell(24) studied cyclic depositional
sequences on a small scale (typically 1-2 m
thickness) not previously recorded and identified
seven ore types characterised by their lithology,
structure, oil yield, organic content and
mineralogy. The prevailing depositional environ
ments were interpreted as shallow lacustrine, with
sub-environments ranging from lacustrine to
pedogenic.
Hutton(25) classified the organic matter in a
range of oil shale types and Table 5 summarises his
scheme for Australian oil shales. The bulk of the
organic matter in the normal oil shale is derived
from algae whereas the organic matter in the brown
coal and carbonaceous shale is derived from higher
plant material and dominated by vitrinite (e.g. in
the Humpy Creek seam of the Rundle deposit(25) and
in the Lowmead deposit (26) ) .
Sherwood and Cook(27) and Glikson(28) described
petrology and electron microscopy studies of the
Toolebuc and other oil shales, which were generally
consistent with Table 5. Glikson indicated a major
cyanobacterial contribution to the Toolebuc and
Cambrian Camooweal oil shales, corresponding to
their formation under anoxic conditions.
The petrographers have suggested that their
science not only provides data about the origin
of the oil shale but can also contribute to an
understanding of its processing properties,
whereas chemists have made little use of this
information. Khorasani(29) claimed that X-ray
diffraction and electron microscopy were more
informative than petrology for the character
ization of organic matter in oil shales. In
yet another approach, Rigby et al.(30) showed
that Australian oil shales can be categorised by
their l^N/^N ratios and related to their
environment of deposition, consistent with
Hutton's petrographic classification.
The organic geochemical characteristics of
the Toolebuc Formation and the Julia Creek
deposit, in particular, have been extensively
investigated(31-34). Dale et al.(32) found that
the trace elements of environmental interest
(e.g. As, Se, Cd, Sb, U) are resident in the
sulphide minerals pyrite, sphalerite and
chalcopyrite, and there is a strong correlation
between them and the kerogen. Vanadium (0.2-0.3
wt %) occurs in clay minerals, as hydrated
oxides or vanadates and as organo-vanadium
complexes, but the high acid consumption in
leaching appears to preclude economic
recovery(34).
Fookes and Loeh(35) have separated a large
number of nickel and vanadyl porphyrins from
TABLE 5. CLASSIFICATION OF ORGANIC MATTER IN AUSTRALIAN OIL SHALES(25)
Type of Shale
Dominant Organic
Matter
Precursors
Other Organic
Matter
Torbanite
telalginite
Botryococcus
vitrinite
inertinite
Lamosite
lamalginite
Pediastrum
telalginite
vitrinite
sporinite
bitumen
Marinite
bituminite
lamalginite
acritarchs
telalginite
vitrinite
sporinite
resinite
Tasmanite
telalginite
Tasmanites
lamalginite
Deposit Alpha
Glen Davis
Joadja
Newne s
Condor
Duaringa
Lowmead
Nagoorin
Rundle
Stuart
Toolebuc
Formation
MerseyRiver
166
Julia Creek oil shale and shown that they are
derived from chlorophyll. This represents the first
complete proof of Treibs'
hypothesis, formulated
almost 50 years ago, that the metalloporphyrins in
crude oil and fossil fuels are derived from
chlorophyll and therefore of biological origin.
Trace element characterization of the Condor,
Rundle and Nagoorin deposits has also been
reported(36) .
The concentrations of naturally occurring
radioactive elements in Australian oil shales are
similar to or less than the published data for soils
and shale bodies except for the uranium concentra
tion in Julia Creek oil shale which is 15-30 times
higher(37).
BENEFICIATION
Attempts at the beneficiation of Australian oil
shales have generally been unsuccessful. Moore and
Thompson(38) reported that wet beneficiation of
Rundle shale is technically feasible; however,
because of the hygroscopic and porous nature of the
oil shale and claystone mixtures, the cost of
removing water absorbed during beneficiation offsets
the advantages in feed grade improvement. O'Brien
(39) attempted beneficiation of Stuart oil shale by
bench-scale flotation, crushing/screening, grinding/
screening and gravity separation. A satisfactory
flotation process was not developed, even with a
-22 /um feed. The best flowsheet involved crushing,
wet tumbling, desliming, screening and specific
gravity concentration and gave 75% organic recovery
in 50% of the original weight.
McLaren(40) attempted beneficiation of Julia
Creek oil shale by carbonic acid extraction of the
carbonate minerals at pressures up to 5.2 MPa and
temperatures up to 200C. No kerogen was liberated
and only small amounts of kerogen-enriched material
were freed by these treatments.
Sowerby et al.(41) investigated the use of
nuclear techniques for the on-line analysis of
Rundle oil shale on conveyor belts as a means of
rejecting low grade material. The most favourable
approach appeared to be neutron inelastic scattering
for the determination of carbon content. A set of
26 samples representing eleven ore types at Rundle
gave an r.m.s. deviation of 7.7 L t~l between the
Fischer assay and the oil yield calculated from
total carbon content.
RETORTING CHEMISTRY
The retorting chemistry of Australian oil shales
differs significantly between shales particularly
the carbonaceous and normal shales and, by
comparison, from Green River shales. Ekstrom et
al.(42) investigated the kinetics of oil and gas
formation following the method of Campbell et
al.(1980). The kinetics of oil formation for the
Condor, Duaringa, Stuart and Nagoorin
carbonaceous oil shales were similar to those of
Green River shale with an activation energy in
the range 200-232 kJ mol-1 for a single
decomposition process. With Condor carbonaceous,
two approximately equal (for oil yield) processes
for oil formation were observed. Hydrogen
evolution for the Condor and Duaringa deposits
resembled that for Green River shale with a peak
at460
C, close to the temperature at which oil
formation was at a maximum, but also occurred at
higher temperatures under secondary pyrolysis
conditions with the carbonaceous shales. The
Condor, Duaringa and Nagoorin carbonaceous
deposits all evolved significant carbon dioxide
at temperatures as low as150
C, presumably from
the decomposition of unstable components of
kerogen.
Levy and Stuart(44) found with Nagoorin and
Condor carbonaceous shales that the aliphatic
constituents of the kerogen were completely
removed in the first half of the pyrolysis
process, whereas with Rundle and Condor brown
shales alkyl groups were still present after
80 per cent decomposition of the kerogen.
Fookes and Johnson(45) pyrolysed a range of
model compounds (based on the hypothesis that
kerogen consists of n-alkyl chains attached to an
involatile aromatic nucleus) and compared the
products and kinetics of their decomposition with
data obtained from oil shales. Phenyl
dodecanoate -
0^CO<CH2>1OCH-
was considered to be a good model of the kerogen
in carbonaceous shale.
Corino and Turnbull(46) have measured the
heats of pyrolysis of a range of Rundle oil shale
materials and also of the associated individual
clay minerals, as well as the heats of combustion
of fresh, partially pyrolysed and spent shales to
generate data for heat balance calculations.
Lynch et al.(47) used proton nuclear
magnetic resonance thermal analysis to study
167
changes in oil shale pyrolysis. They identified two
regions of enhanced molecular mobility, one at
~330C attributed to a possible "glass to rubber
transition"
and the second just before the main
pyrolysis step (~430C) and attributed to
"softening"of a relatively stable component of the
kerogen. Differences observed in the pyrolysis
behaviour of the series of oil shale lithotypes
identified by Coshell(34) in the Rundle deposit were
attributed to interactions between the inorganic
matrix and the kerogen rather than to variations in
the kerogens(48) .
Hurst and Ekstrom(49) used electron spin
resonance to study the formation and decay of free
radicals during pyrolysis of Condor normal and
carbonaceous shales. Although the initial free
radical concentration was similar for both kerogens,
rapid heating of the aromatic carbonaceous material
resulted in a much larger transient radical
concentration than that found for the more aliphatic
normal shale. This process occurred at about580
C,
which is much higher than that required for oil
formation, and is attributed to the formation and
further aromatization of the carbon residue formed
during oil production.
Lambert et al.(50) showed that the
aromaticities of Rundle shale residues increased
with increasing reaction temperature and time
whereas the aromaticities of the oils were
essentially independent of these conditions. Up to
25 per cent of the original aliphatic carbon was
converted to aromatic components in the residue at
500C.
Regtop et al.(51) passed aliphatic compounds
(alkanes, alkenes, alkanoic acids, ketones, alcohols
and amines) through beds of spent shales, clays and
charcoal at temperatures in the range300-
600
C and
showed that all the materials catalysedisomerisa-
tion, aromatisation and cracking reactions to
varying degrees. Thus, although an aromatic kerogen
can be expected to give a largely aromatic oil, some
of the aromatic products could well be derived from
secondary reactions of the initial volatile products
in contact with spent shale.
RETORTING PROCESSES
The overall stoichiometry of oil shale pyrolysis
under material balance modified Fischer assay
conditions has been reported for the Condor,
Duaringa and Stuart deposits(52,53) . Organic carbon
conversion to oil ranged from 43% for the lowest
grade sample (Duaringa) to 63% for the highest
grade sample (Stuart). For Stuart shale, Gannon
et al.(53) showed that the organic carbon
concentrations in fresh and spent shale were
linearly related to oil yield, but the organic
carbon conversion to oil was not linear,
reaching an asymptotic limit of 62% above an oil
yield of ~100 LTOM (litres per tonne at 0%
retort water).
Wall (54) investigated the retorting of
Condor, Julia Creek and Rundle shales at 500C
in superheated steam in static and fluidised
beds (42 mm i.d.) and compared the results with
Fischer assays under identical heating
conditions. Oil yields were enhanced by steam
sweeping from 7% for Rundle to 29% for Condor
shale. Fluidised bed pyrolysis in superheated
steam with flash heating gave similar results
(55). The heating rate had no effect on oil
yield. There was no evidence for chemical
interaction between the steam and kerogen, and
the results suggested that steam promotes oil
evaporation from the shale and reduces the
extent of oil coking within the shale particles.
In subsequent experiments with Condor oil
shale, nitrogen fluidisation, flash heating and
long residence times, Dung and Wall (56) found
that the oil yield was constant in the
temperature range 450 to 525C, and about 10 per
cent in excess of Fischer assay. The additional
oil was mainly a high boiling point fraction
(450 to 6008C). The oil yield decreased with
temperature from 525 to600
C where thermal
cracking of the oil vapour became significant.
Schafer(57) also reported enhanced oil
yields under nitrogen-fluidised, flash heating
conditions compared with slow heating for
Condor, Julia Creek and Rundle oil shales.
Ekstrom et al.(58) studied the hydro
retorting of Nagoorin, Rundle and Mt. Coolon oil
shales at 550C with hydrogen pressures up to
6 MPa. The carbonaceous Nagoorin and Mt. Coolon
shales gave oil yields equivalent to 350% of
Fischer assay, whereas no significant effect was
observed for Rundle oil shale. The increase in
yield was accompanied by a marked increase in
the aromaticity of the oil and the content of
phenol and its derivatives. For example, the
Nagoorin oil produced at 6 MPa hydrogen had a
carbon aromaticity of 68% and a proton
168
aromaticity of 29%. This shale oil was similar to
coal pyrolysis liquids and compounds such as
naphthalene, anthracene and phenanthrene, could be
readily identified. Retorting under the same
pressure of nitrogen did not affect the yield or the
composition of the oil.
Preliminary laboratory scale data on the
kinetics of oil shale pyrolysis have been reported
by Charlesworth(59) , and Wall and Dung(60) for
Rundle and Condor shales, respectively. Charlesworth
used the flame ionisation detector (FID) of a gas
chromatograph to monitor the continuous rate of
evolution of hydrocarbons whereas Wall and Dung have
developed a new method which simultaneously produces
yield versus time data in a series of experiments of
different duration for all of the pyrolysis
products, and also provides oil and spent shale
samples for analysis. Wall and Dung(60) found that
oil formation was a first order process whereas the
rates of evolution of product gases deviated
markedly from first order behaviour. Charlesworth
(59) found that the evolution of total hydrocarbons
was not a first order process.
THEORETICAL MODELLING OF RETORTING
Researchers at the University of Queensland have
put a substantial effort into modelling the drying
and retorting of oil shale, particularly under
fluidised bed conditions(61-63) . Do(63) described a
theoretical model for the pyrolysis of large oil
shale particles in an isothermal fluidized bed
retort based on the two-step reaction network of
Wallman et al.(64), with the addition of the
cracking reactions of heavy and light oil. The
cracking kinetics of Burnham(65) were assumed. The
analysis described the pore diffusion and chemical
reaction inside the shale particles to give the
final distribution of products, and also the dynamic
response of these species from the onset of
operation. The theoretical prediction of the final
products, as a function of temperature, agreed well
with the experimental data of Wallman et al.(64).
Litster et al.(61) described models for the
fluidized bed drying and retorting of Rundle oil
shale particles. Their drying model, based on
constant rate drying, predicted the final moisture
content well for values above 4% but would have to
be augmented for diffusion-controlled mass transfer
at lower values. A retorting model based on a
simple global first order decomposition reaction
(with kinetic parameters determined from non-
169
isothermal batch fixed bed experiments),
residence time distributions, particle balances
and corrected for cracking in the freeboard
above the bed gave good agreement with gas
yields and fair agreement with oil and coke
yields.
Peshkoff and Do(62) developed mathematical
models for three flow regimes: co-current oil
shale retorts operating under isothermal and
non-isothermal conditions, and isothermal
counter-current operation. The counter-current
isothermal retort was reported to have a
superior oil yield because the vapour residence
time and opportunity for cracking reactions are
reduced.
GASIFICATION OF SPENT SHALE
The reactivity of a number of Australian
spent oil shales to air, steam and carbon
dioxide has been investigated(66,67) . Whereas
the organic carbon concentration is less than
10 wt % from the retorting of normal oil shales,
concentrations of 40-80 wt % are obtained from
the retorting of carbonaceous shales which are
significantly more reactive.
Charlton(66) investigated the fluidized bed
combustion of a porous, low residual carbon
(1.9 wt %) Rundle spent shale in the temperature
range 650-750C and found an activation energy
of 97 kj mol-l, in agreement with Sohn and
Kim(68) for Colorado spent shale. The data were
correlated well using the version of the
generalised grain model developed by Sohn and
Bascur(69).
Jones and Sandars(67) studied the kinetics
of reaction of oxygen, carbon dioxide and steam
with carbonaceous Condor and Nagoorin spent
shales containing 41 and 81 wt % organic carbon,
respectively, in a thermobalance at temperatures
up to 500C. Their activation energies in air
were in the range 108-125 kJ mol~l including
experiments with oxygen partial pressures as
high as 1.3 MPa. They used the random pore
model of Bhatia and Perlmutter( 70) which was
consistent with the apparent initial increase in
reaction rate with conversion at low pressures
and the pore structure insensitive behaviour of
the samples at high pressures.
Jones and Sandars also determined activation
energies for reactions with carbon dioxide and
steam. For the high carbon content Nagoorin
spent shale, values of 242 and 140 kj mol"1,
respectively, were obtained which are of the same
order as values reported for coal chars. For Condor
carbonaceous spent shale, lower values of 176 and
115 kJ mol-1
were obtained (67) .
PROCESS DEMONSTRATION STUDIES
The largest scale oil shale processing research
in Australia is being carried out in process
demonstration units (typically 5-30 kg h~l) in the
laboratories of the University of Queensland, the
CSIRO Divisions of Energy Chemistry and Mineral
Engineering and CSR Ltd. Do et al.(71) briefly
described the first of these facilities which
incorporates a 100 mm square fluidized bed retort
and 300 mm square spent shale combustor. Dung et
al.(72) outlined the second facility which is based
on 154 mm diameter fluidized bed reactors for
retorting and combustion and is currently being
commissioned.
CSR Ltd has operated a 200-500 kgd-1
horizontal screw retort in Sydney since the 1970s
and this is being integrated with fluidized bed
combustion studies in a 300 mm diameter reactor at
theCSIRO1
s Clayton laboratories( 18) . No experi
mental data from these studies have been published
apart from supporting laboratory studies of the
reaction chemistry of the CSR/CSIRO process (e.g.
73-75).
Potter et al.(76) have considered the energy
balance around a Lurgi-Ruhrgas retort as part of
their design studies and suggested a variety of ways
of reducing the energy consumption via the use of
fluidized beds for solid-solid heat exchange,
multiple effect drying with super-heated steam, and
co-pyrolysis of shale and coal.
ANALYSIS AND UPGRADING OF SHALE OIL
Knowledge of the detailed composition of crude
shale oils is a useful starting point for the
development of process flowsheets. Rovere and
co-workers (77) have, for example, reported the
detailed chemical analysis of Condor shale oil and
identified more than 600 compounds. Their
analytical procedure used open column chromatography
to separate the oil into a large number of fractions
which were then examined by gas chromatography/mass
spectrometry (GC/MS).
Upgrading studies have concentrated on the Julia
Creek and Rundle shale oils (Table 6). Collabora
tive CSR/CSIRO studies(8,79,80) of the upgrading of
Julia Creek shale oil to transport fuels have
TABLE 6. TYPICAL ANALYSES OF SHALE OILS
Julia Creek Rundle
Primary Topped 100-400C
emental Analysis Naphtha Crude Fraction
Carbon, wt % 81.7 75.0 85.4
Hydrogen, wt % 11.4 9.1 11.5
Nitrogen, wt % 0.26 1.9 1.1
Oxygen, wt % 0.32 8.6 0.9
Sulfur, wt % 6.2 5.5 0.91
H/C 1.66 1.46 1.61
lE Aromaticity (%) 9.3
Reference (8)
16.2
(8)
6.2
(78)
170
confirmed that aviation turbine fuel and
automotive diesel fuel can be produced from
topped (196C - FBP) crude shale oil by
hydro-stabilisation and further hydrotreatment
of the secondary distillate(8,80) . Although
the naphtha fraction (20% of whole oil)
contained almost 25% thiophenes, hydrotreatment
at 350C with commercial Ni-Mo catalysts readily
removed the majority of the components contain
ing heteroatoms without significantly affecting
the aromaticity. Further upgrading by
isomerisation and reforming should produce a
specification unleaded gasoline(8).
Harvey et al. (78,81) investigated hydro-
treatment of a fraction of Rundle shale oil
boiling in the range100-400
C, which
constituted 70% of the whole oil, with three
commercial catalysts. A Ni-Mo catalyst was the
most effective but it did not provide sufficient
reduction in nitrogen content (particularly
pyrrolic nitrogen compounds), nor sufficient
hydrocracking, to produce good yields of middle
distillate; the product was therefore only
suitable as a substitute crude oil. A new
catalyst has been developed with a much greater
ability for nitrogen removal and hydrocracking.
In its most active configuration, it is a
ternary metal combination of ruthenium,
molybdenum and nickel supported on a mixture of
y-alumina and Y-zeolite.
As a result of preliminary laboratory
experiments, Barrett et al . (82) reported that
vacuum distilled residues (280-320C) of Julia
Creek shale oil have properties similar to
natural petroleum bitumens and could be marketed
as road-making bitumen.
ENVIRONMENTAL STUDIES
The composition of leachates of both fresh
and spent shale has been investigated in batch and
column leaching tests, including both saturated and
unsaturated conditions for the latter(83-86) . Most
of the leachable salts (sulphates and chlorides of
Ca, Mg, Na and K) are readily removed in the first
few pore volumes of eluted leachate. Under
unsaturated conditions, these salts are readily
dissolved at the wetting front and transported by it
with little longtitudinal dispersion(86) . Krol et
al.(87) have developed a model of leachate flow in a
spent oil shale heap under unsaturated flow
conditions which takes into account liquid and
solute transport, leaching kinetics, ion exchange
and chemical equilibrium considerations for the
major inorganic ion species.
Heavy metal elements of possible environmental
concern in these leachates include As, Cu, Cd, Mn,
Ni and Zn (84). Chapman et al.(88) have studied the
transport of As, Cu, Ni and Zn under simulated
conditions in a creek bed on the Rundle prospect and
found that mobility increased in the orderCu2+ <
Zn2+<Ni2+<As043-
< acidity.
The composition of retort water from Fischer
assays of Rundle shale has been reported previously
(83) based on capillary column GC/MS/FID analysis
of fractions obtained by methylene chloride
extraction. Batley(89) analysed retort waters from
Condor, Julia Creek, Nagoorin and Rundle shales
using high precision liquid chromatography with
electrochemical detection and found that it offered
improved selectivity and sensitivity over
conventional u.v. absorbance detection. Dobson et
al.(90) investigated capillary column GC/MS for the
analysis of major organic components in monitoring
processes for the treatment of retort waters and
found that it appears suitable as a semi
quantitative tool but standard screening procedures
are not yet feasible.
Bell and co-workers (83) described attempts to
develop treatment processes for Rundle retort water
and suggested that a combination of stripping,
adsorption and biodegradation would be a viable cost
effective process. Subsequent work has concentrated
on the efficiency of raw and spent shales as
adsorbents for the treatment of retort waters(91,92) .
Results have shown that a significant amount of
organic carbon, much greater than for Colorado
shales, is adsorbed onto both raw and spent Rundle
shales, and is attributed to the larger internal
surface area of Rundle shales. The adsorbed
organics are not easily desorbed. The major
non-absorbing organic components in the retort
waters are the carboxylic acids. Although the
results of this work suggest that co-disposal of
raw water with raw and spent shale is a feasible
proposition, the recent Rundle project
feasibility study indicated that, by careful
water balancing, zero effluent from the plant
may be achievable. This assumed that process
waste water, after stripping to remove volatile
impurities, was recycled to the process for
reuse and the impurities were incinerated in the
spent shale combustor ( 38) .
Revegetation studies (93) have given
excellent results for re-establishing total
vegetation cover and local native forests on the
various wastes from Rundle oil shale mining. The
value of topsoil and the addition of spent shale
to claystone or red clay overburden materials in
supporting vegetation was demonstrated.
CONCLUDING COMMENTS
While initial oil shale research in
Australia concentrated on characterization of
oil shale resources, emphasis is now being given
to the development of processes tailored to
Australian oil shales. This must be followed,
in turn, by a development and demonstration
program, coupled with assessment studies of the
economic, social and environmental factors
involved in such large-scale projects, if
Australia is to have a major oil-from-shale
industry beyond the year 2000.
REFERENCES
1. Esso Australia Ltd, An Esso Report
Australian Energy Outlook, 1984.
2. Department of Resources and Energy,
Compendium of Australian Energy Research,
Development and Demonstration Projects No.
5, Australian Government Publishing
Service, Canberra, 1984.
3. Proceedings of the First Australian
Workshop on Oil Shale, Lucas Heights, 18-19
May 1983.
4. Proceedings of the Second Australian
Workshop on Oil Shale, Brisbane, 6-7
December 1984.
5. Cane, R.F., The oil shales of Australia and
their industrial history, 12th Oil Shale
Symposim Proceedings, Colorado School of
Mines Press, 17-25, 1979.
171
6. Baker, G.L., Australian developments in oil
shale processing, 14th Oil Shale Symposium
Proceedings,Colorado School of Mines Press,
220-234, 1981.
7. Southern Pacific Petroleum NL, Annual Report,
1983.
8. Stephenson, L., Muradian, A., Fookes, C.J.R.,
Atkins, A.R.,and Batts, B.D, Marketable
transport fuels from Julia Creek shale oil,
This Symposium, 1985.
9. Noon, T.A. , Oil shale resources in
Queensland, Ref. 4, 3-8, 1984.
10. Mandeison, J.J., Recent developments in the
Julia Creek shale oil project, Ref. 3, 18-21,
1983.
11. Southern Pacific Petroleum NL/Central Pacific
Minerals NL, Rundle Oil Shale Project, Joint
Announcement, September 25, 1984.
12. Southern Pacific Petroleum NL, Quarterly
Report for the Period ending 30th June, 1984.
13. Olive, R.T., Chui Chong, E. and Dear, J.F.,
The Yaamba oil shale deposit - the resource
and its challenge. Australian Institute of
Energy National Conference 1984, Conference
Papers, Brisbane, 14-19, 1984.
Southern Pacific Petroleum NL/Central Pacific
Minerals NL/Esso Exploration and Production
Inc, Joint Announcement, 15 March, 1985.
Southern Pacific Petroleum NL, Quarterly
Report for the Period to 30 September, 1984.
McCarthy, D.J., Mandeison, J., Sitnai, 0. and
Whitehead, A., Process for the recovery of
oil from shale, Australian Patent 89585/82,
1983.
17. Sitnai, 0., Process concept for retorting of
Julia Creek oil shale, Energy Progress, 4,
100-105, 1984.
18. Tolmie, D.B., Status of Julia Creek shale oil
project, Ref. 4, 20-24, 1984.
19. Alfredson, P.G.,Oil shale research in
Australia, Ref. 4, 25-30, 1984.
20. Ozimic, S., Depositional environment of the oil
shale-bearing Cretaceous Toolebuc Formation and
its equivalents, Eromanga Basin, Australia,
15th Oil Shale Symposium Proceedings, Colorado
School of Mines Press, 137-148, 1982.
21. Green, D.A. , Mclver, R.G.,and O'Dea, T.R.
,
Revised geology of the Condor oil shale
deposit, Ref. 4, 33-37, 1984.
14.
15.
16.
22. Lindner, A.W. and Dixon, D.A., Some aspects
of the geology of the Rundle oil shale
deposit, Australian Petroleum Exploration
Association Ltd Journal, ^^2, 165-172,
1976.
23. Ivanac, J.F., Stuart, Nagoorin-Nagoorin
South, Lowmead and Duaringa oil shale
deposits: a review, Ref. 3, 12-17, 1983.
24. Coshell, L., Cyclic depositional sequences
in the Rundle oil shale deposit, Ref. 3,
25-30, 1983.
25. Hutton, A.C, Organic petrography of
Rundle-Stuart lamosite -
a case study,
Ref. 3, 31-34, 1983.
26. Henstridge, D.A. and Hutton, A.C, The
geology and organic petrography of the
Lowmead oil shale deposit, Ref. 4, 38-43,
1984.
27. Sherwood, N.R. and Cook, A.C, Petrology of
organic matter in the Toolebuc Formation
oil shales, Ref. 3, 35-38, 1983.
28. Glikson, M.,The organic matter in oil
shales: its nature and origin, Ref. 3,
39-42, 1983.
29. Khorasani, G.K., Characterization of
organic matter in oil shales: application
of X-ray diffraction technique and electron
microscopy, Ref. 4, 62-66, 1984.
30. Rigby, D., Batts, B.D. and Smith, J.W. , The
characterization of Australian oil shales
by nitrogen isotope abundances, Ref. 4,
103-107, 1984.
31. Boreham, CJ. and Powell, T.G., The
Toolebuc oil shale: an organic geochemical
investigation, Ref. 4, 50-55, 1984.
32. Dale, L.S., Fardy, J.J., Patterson, J.H.
Ramsden, A.R. , Abundances and mineralogy of
trace elements in Julia Creek oil shale,
Ref. 4, 85-90, 1984.
33. Saxby, J.D., The distribution, properties
and potential of Toolebuc oil shale, Ref.
3, 43-46, 1983.
34. Riley, K.W., Vanadium in the Toolebuc oil
shale and possibilities for recovery from
spent shale, Ref. 3, 65-68, 1983.
35. Fookes, C.J.R. and Loeh, H.J. , Porphyrins
of Australian oil shales: a nuclear
magnetic resonance study,, Ref. 3, 65-68,
1983.
172
36.
37,
38.
39.
40.
41,
42.
43.
44.
45.
46.
47,
48.
49.
50.
Dale, L.S. and Fardy, J.J., Trace element
characterization of oil shales, Ref. 3, 57-60,
1983.
Fardy, J.J. and Brockbank, C.I., Radioactivity
of Australian oil shales, Ref. 4, 108-113, 1984.
Moore, A.J. and Thompson, B.J., Status of
technical development of the Rundle oil shale
project, Ref. 4, 9-14, 1984.
O'Brien, B.A., Beneficiation of Stuart oil
shales, Ref. 4, 78-82, 1984.
McLaren, K.G. , Kerogen-minerai bonding and
beneficiation studies with a carbonate oil
shale, using carbonic acid attack and a novel
explosive disintegration technique, Fuel
Processing Technology, in press, 1985.
Sowerby, B.D., Davies, K.E. and Baker, L.A.,
Nuclear techniques for the on-line bulk
analysis of Rundle oil shale, Ref. 3, 91-94,
1983.
Ekstrom, A., Hurst, H.J. and Randall, CH.,The
chemical and retorting properties of selected
Australian oil shales, Ref. 3, 123-126, 1983.
Campbell, J.H., Koskinas, G.J., Gailigos, G.
and Gregg, M.,Gas evolution during oil shale
pyrolysis. Non-isothermal rate measurements,
Fuel, JJ9, 718-726, 1980.
Levy J.H. and Stuart, W.I., Characterisation
of Australian oil shales by thermal methods,
Ref. 4, 91-96, 1984.
Fookes, C.J.R. and Johnson, D.A., An investi
gation of the primary reactions in the
pyrolysis of kerogens, Ref. 4, 176-181, 1984.
Corino, G.L. and Turnbull, A.G., Calorimetric
studies of oil shales and shale products, Ref.
4, 97-102, 1984.
Lynch, L.J., Webster, D.S. and Parks, T.,
Proton nuclear magnetic resonance thermal
analysis of oil shales, Ref. 3, 139-142, 1983.
Parks, T., Lynch, L.J. and Webster, D.S., A
comparison of the pyrolysis behaviour of Rundle
oil shale ore types by *H NMR thermal analysis,
Ref. 4, 153-158, 1984.
Hurst, H.J. and Ekstrom, A., An electron spin
resonance study of oil shale retorting, Ref. 4,
159-163, 1984.
Lambert, D.E., Wilson, M.A. and Collin, P.J.,
Conversion of aliphatic to aromatic carbon
during pyrolysis of Rundle oil shale and the
characterization of oil products, Ref. 4,
164-169, 1984.
51,
52,
53.
54.
55.
56.
57.
58.
59.
60.
61,
62.
63.
Regtop, R., Ellis J., Crisp, P.T., Ekstrom,
A. and Fookes, C.J.R. ,Oil shale pyrolysis
mechanisms, Ref. 4, 170-175, 1984.
Gannon, A.J. and Henstridge, D.A.,Kerogen
conversion relationships for selected
Australian oil shales, Ref. 4, 123-128,
1984.
Gannon, A.J. , Henstridge, D.A. and
Schoenheimer, A.N.
,Stuart oil shale
deposit -
relationships of organic carbon
with shale oil yields, Ref. 3, 101-104,
1983.
Wall, G.C, Static and fluidised bed
pyrolysis of Australian oil shales, Ref. 3,
105-108, 1983.
Wall, G.C, Isothermal fluidised-bed
pyrolysis of Australian oil shales in
superheated steam, 17th Oil Shale Symposium
Proceedings, Colorado School of Mines
Press, 300-309, 1984.
Dung, N.V. and Wall, G.C, Fluidised bed
pyrolysis of Condor oil shale-
a laboratory
scale study, Ref. 4, 200-205, 1984.
Schafer, H.N.S., Flash pyrolysis of Rundle,
Julia Creek and Condor oil shales, Ref. 3,
109-112, 1983.
Ekstrom, A., Fookes, C.J.R. and Wong, K. ,
The retorting of Rundle, Mt Coolon and
Nagoorin oil shales under high pressure
hydrogen and nitrogen, Ref. 4, 135-140,
1984.
Charlesworth, J.M.,The rate of evolution
of organic molecules from Australian oil
shales under isothermal conditions, Ref. 3,
127-130, 1983.
Wall, G.C. and Dung, N.V., The isothermal
pyrolysis kinetics of Condor oil shale,
Ref. 4, 129-134, 1984.
Litster, J.D., Rogers, M.J. and Newell,
R.B., Modelling fluid-bed drying and
retorting of Rundle oil shale, Ref. 4,
206-211, 1984.
Peshkoff, E. and Do, D.D., Modelling of a
continuous retort for oil shale pyrolysis,
Proceedings 12th Australian Chemical
Engineering Conference, Melbourne, 439-444,
August, 1984.
Do, D.D., Modelling of oil shale pyrolysis
in a fluid-bed retort, Fuel Processing
Technology, 10, 57-76, 1985.
173
70.
71
64. Wallman, P.H., Tamm, P.W.,and Spars, B.G., Oil
shale retorting kinetics, ACS Symposium Series,
163, 93-113, 1981.
65. Burnham, A.K., Chemistry of shale oil cracking,
ACS Symposium Series, 163, 39-60, 1981.
66. Charlton, B.G., The fluidised bed combustion
kinetics of Rundle oil shale char, Ref. 4,
224-229, 1984
67. Jones, C.K.S. and Sandars, G.A.
,The
gasification potential of some Australian spent
oil shales, Ref. 4, 212-217, 1984.
68. Sohn, H.Y. and Kim, S.K., Intrinsic kinetics of
the reaction between oxygen and carbonaceous
residue in retorted oil shale, Ind. Eng. Chem.
Process Des. Dev., 1_9, 550-555, 1980.
69. Sohn, H.Y. and Bascur, O.A., Effect of bulk
flow due to volume change in the gas phase on
gas-solid reactions: initially porous solids,
Ind. Eng. Chem. Process Des. Dev., 2\_, 658-663,
1982.
Bhatia, S.K. and Perlmutter, D.D., Unified
treatment of structural effect in fluid-solid
reactions, AIChE J, 2j), 281-289, 1983.
Do, D.D., Litster, J.D. , Peshkoff, E. , Newell,
R.B. and Bell, P.R.F., Pyrolysis of Queensland
oil shale in a fluidized bed: modelling and
experimental studies, Ref. 3, 131-134, 1983.
72. Dung, N.V., Wall, G.C, Coles, D.R. and Kastl,
G.,Fluidised bed pyrolysis of Australian oil
shales- the design and operation strategy for
a 2-30 kg/h process development unit, Ref. 4,
199, 1984.
73. Grave, N.C, McCarthy, D.J. and Poynton, H.J.,
Recarbonation of lime in ash from Julia Creek
oil shale and related process factors, Ref. 4,
194-198, 1984.
McCarthy, D.J., Kinetics of decomposition of
CaCO^ in an Australian oil shale, Fuel, 62,
1238-1239, 1983.
McCarthy, D.J. and Poynton, H.J., Formation of
calcium silicates during processing of Julia
Creek oil shale, Fuel, j>3, 769-773, 1984.
Potter, O.E., Fryer, C, Christiansen, G. ,
Cunico, P., Swaine, G., Tam, K.C, Preslmaier,
R. and Hoskin, CM., New variations on the old
theme of shale oil recovery, Ref. 4, 188-193,
1984.
77. Rovere, C. , Ellis, J., Crisp, P.T. and Bolton,
P.D., Chemistry of Condor shale oil, Ref. 3,
161-164, 1983.
74.
75.
76.
80.
81
82.
83
84
174
78. Harvey, T.G., Matheson, T.W. , Pratt, K.C.
and Stanborough, M.S., Catalytic upgrading
of Australian shale oils, Proceedings 12th
Australian Chemical Engineering Conference,
Melbourne, 455-462, August 1984.
79. Fookes, C.J.R. and Atkins, A.R. , Upgrading
Julia Creek shale oil naphtha to gasoline,
Ref. 4, 245-250, 1984.
Muradian, A. and Stephenson, L., Jet and
diesel fuels derived from Julia Creek shale
oil, Ref. 4, 239-244, 1984.
Harvey, T.G., Matheson, T.W. , Pratt, K.C.
and Stanborough, M.S., Catalyst development
for upgrading Australian shale oils, Ref.
4, 251-254, 1984.
Barrett, D., Brenchley, R. and Day, C, The
potential of shale oil residues for bitumen
production, Ref. 3, 169-172, 1983.
Bell, P.R. , Greenfield, P.F. and Nicklin,
D.J., Chemical and physical characterization
of effluent streams from the processing of
Australian oil shale, 16th Oil Shale
Symposium Proceedings, Colorado School of
Mines Press, 477-486, 1983.
Batley, G.E., Composition of oil shale
leachates and process waters, Ref. 3,
179-182, 1983.
85. Jones, D.R. and Chapman, B.M., An investi
gation of the leaching behaviour of solid
wastes from Rundle oil shale, Ref. 3,
183-186, 1983.
Geronimos, C, Bell, P.R.F., Krol, A.,
Greenfield, P.F. and Dunstan, M.J.,
Comparisons of leachates produced from
laboratory columns and a weathering column
and a weathering column exposed to field
conditions, Ref. 4, 276-281, 1984.
Krol, A.A., Bell, P.R.F. and Greenfield,
P.F., Development of a model for leachate
flow and composition from a column of spent
oil shale, Proceedings 12th Australian
Chemical Engineering Conference, Melbourne,
137-144, August 1984.
Chapman, B.M., Jones, D.R. and Jung, R.F.,
Transport of metals of environmental
interest released into a creek bed on the
Rundle oil shale prospect, Ref. 4, 270-275,
1984.
Batley, G.E., Applications of liquid chroma
tography with electrochemical detection to
86
87
88
89
the analysis of oil shale process waters and
leachates, 17th Oil Shale Symposium
Proceedings, Colorado School of Mines Press,
352-358, 1984.
90. Dobson, K.R. , Greenfield, P.F., Corney, M.W. 92.
and Bell, P.R.F., The suitability of capillary
column gas chromatography for the routine
evaluation of retort water composition, Ref.4,
294-299, 1984.
91. Bell, P.R.F., Greenfield, P.F., Corney, M. and 93.
Moore, A.J., Evaluation of Rundle spent shale
as an adsorbent for the treatment of retort
water, 17th Oil Shale Symposium
Proceedings, Colorado School of Mines
Press, 318-328, 1984.
Bell, P.R.F., Greenfield, P.F., Corney, M. ,
Taylor, T. and Moore, A.J. , Effectiveness
of raw and spent Rundle shales as
adsorbents for the treatment of retort
water, Ref. 4, 282-287, 1984.
Marshall, J.K., Assessment of revegetation
experiments at Rundle, Ref.4, 265-269,1984.
175