MS

31

International Journal ofMass Spectrometry and Ion Physics,, 48 (1983) 31-34 Elsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

ANALYSIS

J.

OF AUSTRALIAN

SHALE

OILS

BY GC/MS

P. BARTLEY

Department

of Chemistry,

Q.I.T.,

G.P.O.

Box 2434,

Brisbane,

Australia

ABSTRACT Oils have been obtained from shale samples from the two major Australian After fractionation by acid/base deposits - those at Rundle and Julia Creek. extraction and chromatography the aliphatic fraction was examined by GC/MS. While the Rundle sample contained mostly n-alkanes with a slight preference for odd carbon number, the Ju1 ia Creek sample contained a large proportion Pristene was present in significof alkenes with no carbon number preference. ant amount in the Julia Creek sample but was almost undetectable in that from RundIe.

INTRODUCTION has been estimated

It shale

oil exceed

in Australia shale

and

deposits

largest contains The

may

reserves

The Julia Basin

is consistent organic

matter

deposit

is present

the Rundle

recoverable reserves

resources

as an alternative

under

are located

reserves

have in that

energy

of

been found country

source.

in Queensland.

The

two

Each

occurs

shallow

and

within

lacustrine

matter

the Toolebuc

period.

in a shallow

as fine grained a much

saline

the organic

conditions

consists

of thin

alginate).

Cretaceous

deposition

but contains

carbonates, than

with

petroleum

Creek,

Period

(lamellar

and is of the early

total

extensive

x lo6 tonnes.

was deposited

debris

Creek

of the poor

significant

the Tertiary

of algal

the worlds

Reasonably

and Julia

of 4000

shale

(ref. 2) during laminae

become Rundle

1) that

bbls.

in the light

deposits, Rundle

(ref.

30 x 1OI2

higher

The

Limestone

phyiscal

marine

environment

lamellar

alginate

content

of higher

of the Eromanga

nature

of the shale

(ref. 2).

The

interbedded

plant-derived

with macerals

sample.

EXPERIMENTAL Oil shale

samples

from

the Kerosene

from

these

samples

representative A sample Lurghi

were

Creek

obtained

seam

of the

at Rundle

by Fischer

of the region Rundle

Ruh.rgas for Southern

OOZO-7381/83/0000-0000/$03.00

from

assay

the Jul ia Creek (30 samp les).

and

the oil

reg ion

Shale

samples

(24 samples)

and

oil was obtained

poo led to obtain

a sample

in question.

shale

was

Pacific 0

also processed Petroleum

in a Lurghi

and a sample

1983 Elsevier Scientific

type

reactor

of the middle

Publishing Company

oil

by

32 obtained.

The analytical

Samples methane

of each

and extracted

extracted

with

until

neutral,

ation

through

where

necessary

neutral

dried

with

MgS04

and

The

with

(2.5 g) was

then adsorbed

silica

a stream

gel

organic

removed traces

of dry onto

volume

organic

remaining

The last

by flushing

with

The

the solvent

column.

are reported

an equal

(3 x 20 ml).

(3 x 20 ml ).

with

oils

with

layer layer

was washed distill-

of sol vent were

a column

removed

An aliquot

composed

as a slurry

1.

was then

by atmospheric

nitrogen.

(230 g) packed

in table of dichloro-

of each

of alumina

into a glass

(3.5 x 70 cm).

Fractions methanol.

were Only

GC/MS

a glass

under

jet

eluates

performed

silica

with

are discussed

Erba column

The magnet

stream which

was

4X computer

using

Kratos

double

4160

of 1OO:I

temperature

and

spectrothrough Samples

onto

a 50 m

programmed

at 1 set/decade

interface

mass

was coupled

gas chromatograph.

splitting

was

scanned

DS-55

chloroform

focussing

instrument

Fractorap

of 1 yl with

capillary

The

cyclohexane, in this paper.

MS-25

at 70 eV.

via a 200 kHz preprocessor

Nova

pentane,

on a Kratos

to a Carlo

at 4oC min-I.

was digitized General

was

by injection

fused

40 to 2900

by elution

E.I. conditions

separator

analyzed

OVl WCOT

obtained

the pentane

analysis

photometer

from

and the data

and processed

by a Data

software.

1

Analytical

Data

.Rundle {Lurgi) Rundle {Fischer) Julia Creek (Fischer)

*

for the three

2M NaOH

a 50 cm vigreux

(230 g) overlayed

TABLE

figures

(25 g) were diluted

0.5M HCl

extract

column

were

oil

CPI

wt % 6

H

N

0

S

Atomic H/C

tliphatic

CPI*

84.60 81.81 81.86

11.30 11.52 9.32

0.88 1.09 I.95

2.40 4.07 0.30

0.82 1.51 6.57

1.60 1.69 1.37

45 40 21

1.25 1.20 0.94

1 + ccn+l

'=

, n = 25, 27, 29, 31 I

DISCUSSION The aliphatic ition

although

higher

(25%)

in the C-24 land

the Fischer (Fig. la).

and C-32

preference

based

maturation (ref. 5,6).

of the two Rundle assay

The aliphatic

al kanes.

1-alkenes carbon

fractions

region

index

sample

fraction

There with

(CPI).

plants

(ref. 3,4),

of the

original

samples

showed

a slightly

consists

mainly

is a considerable a slight

This

could

however,

kerogen

odd/even be taken

it has been

precursors

were

leads

very

similar

large

preference to imply shown

proportion

of n-alkanes

contribution

in composof

(69%) and

from

n-alkanes

indicated

by the

a contribution

that diagenesis

to a decrease

and

in the CPI

from

1. (a) Rundle - aliphatic 1 = l-alkenes; (0 = n-alkanes;

fraction. (b) Julia Pr = pristene).

Fig.

The Julia 1) and

Creek

the aliphatic

{68%)

(Fig.

ments

(ref. 8)

formed pairs

typical

assay

to n-alkanes (ref.

trations

(ref.

observed

12)

that

readily

in the former

The

in the

particularly case

alkenes

to the kerogen low

ution

fram

fatty

acids

plants

in primitive

for

the high sample

than

is much

the Julia

(ref. 5,6). plants

may

weaker Creek

samples

are

shale.

or more

relative

the concen-

this occurs

samples

is much

much

indicates

more

released,

'open' or

(2)

exposed. does

possible

shown

and

9,101

It has been pointed

to be readily samples

Alkane/alkene

(ref.

increase

That

structure

in sedi-

undoubtedly

of l-alkenes

pyrolysis

range.

It is also not have

of alkenes

in the Rundle

(1) the kerogen precursors

proportion

is unusual.

350 o during

samples

(see Table

of n-alkenes

proportion

fraction.

samples

by pyrolysis-GC-MS

in the C1G-CI5

or their

matrix

CPI observed higher

Creek

either

high

of the oil from the

above

- aliphatic

Rundle

in the present

Creek

Julia

the

of the occurence

produced

However,

11).

in the Julia

occluded

production

than

a surprisingly

reports observed

temperatures

of alkenes

that

bonding

during

aliphatic

contains

are few

of chromatograms

more

allowing

fraction

less

and the alkenes

by pyrolysis are

is much

There

lb).

by Fischer

out

oil

Creek

not rule that

the odd/even

out a contrib-

the alkanes dominance

and

34 characteristic

of contemporary

organisms

(ref.

7).

ACKNOWLEDGEMENTS The

author

provision

wishes

to thank

Southern

Pacific

Petroleum

NL and CSR

Ltd

for the

of samples.

REFERENCES 1 2 3 4 5 6 7 8 9 10 11 12

T.F. Yen and G.V. Chilingarin, Oil Shale, Elsevier, Amsterdam, 1976. A.C. Hutton, A.J. Kantsler, A.C. Cook and D.M. McKirdy, APEA Journal, 20 (1980) 44. G. Eglinton and R.J. Hamilton, Chemical Plant Taxonomy, T. Swain (Ed.}, Acad. Press, London, 1963 pp. 187-217. 5.3. Currunins and W-E. Robinson, J. Chem. Eng. Data, 9 (1964) 248. J.W. Jury and E. Eisma, Science, 144 (1964) 1451. W. Henderson, G. Eglinton, P. Siannonds and J.E. Lovelock, Nature, 219 (1968) 1012. J. Han, E-D. McCarthy, W. van Hoevan, M. Calvin and W.H. Bradley, Proc. Nat. Acad. Sci. USA, 59 (1968) 29. J.R. Maxwell, C-T. Pillenger and G. Eglinton, Chem. Rev., 25 (1971) 571. 0. van de Meent, S-C. Brown, R.P. Phitp and B.R.T. Simoneit, Geochim. Cosmochim. Acta, 44 (1980) 999. R.P. Philp, M. Calvin, S. Brown and E. Young, Chem. Geol., 22 (1978) 207. I. Klesment, J. Anal. and Appl. Pyrolysis, 2 (1980) 63. K.D. Bartle, D.W. Jones, H. Pakdel, C.E. Snape, A. Calimli, A. Olcay and T. Tugrul, Nature, 277 (1979) 284.