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.

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