durand and nicaise 1980 - procedures for kerogen isolation

7/27/2019 Durand and Nicaise 1980 - Procedures for Kerogen Isolation

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-

Procedures

for

kerogen isolation

il.

ISOLATION

METHODS

FOR

PHYSICO.CHEMICAL ANALYSIS

Among

the methods used,

we

will

distinguish physical methods

from

chemical

methods.

A. Physical

methods.

Almost all ore dressing

processes

were

used,

i.e. flotation,

ultrasonic

methods,

electroma-

gnetic

and electrostatic

methods,

processes

based on the

wetting

properties

of

OM and

mine-

rais, etc.

[32,

33,

34].

These

processes

are applied

after

fine

grinding

of the

sediment.

Organic fractions

are thus

obtained which should

not, in theory, be chemically altered.

However the rate

of recovery

for

OM

containing small amounts

of minerals

is low,

and

the chemical

composition of

the reco-

vered

fraction

is

rarely

representative of the whole. In order

to improve

recovery it is neces-

sary

to carry out successive

grindings

and

to

repeat

the operations several times, which

is

long

and

costly.

We will however note that, according

to Robinson

[32]

,

use of

a

method

derived

from

that

of

Quass

129,

371has

made it

possibie

to considerably

reduce

(24-99V0)

the

proportion

of the

mineral fraction from oil shales of

various origins. This method

is

based on

wettability diffe-

rences

between

kerogen and the

mineral matrix.

It

consists

in incorporating

water and an oil

phase

(mineral

oil or

n-hexadecane in the cases mentioned) during

attrition

grinding.

The

kerogen

tends

to form

progressively

a

separate

phase

with the oil.

Good

results were

also

obtained

with

Green River Shales by centrifuging

in

a CaCl,

solu-

tion

[32,

36]

with

a

method

based

on

that of Luts

[25].

It

is

easy

to

understand the

lack

of

effectiveness and

general

applicability

of

these methods

in

view

of

the diversity

of

the situations

which

occur. Success cannot therefore

be expected

except in

particular

cases, and

the methods must

be

modified in terms

of the

characteristics

of

the

samples.

B.

Chemical

methods.

Theoretically the objective of these methods is to isolate the kerogen

by

making

the mineral

phase

solubie

while

keeping modifications

in

the chemical composition

of the

OM as

small

as

possible.

They do

in

fact make

possible good

recovery of the

OM

which

is

little

altered

except for

recent

OM

(recent

sediments, soil,

peat,

etc.).

Foliowing the work

of Down

[7]

,

Giedroyc

[4]

and Dancy

[4]

the

methods

now

used are

all

based

upon

the

dissolution of carbonates, sulfides,

sulfates, oxides

and

hydroxides

by HCI

and the dissolution

of

silicates

by HF, after fine

grinding

of

the

rock

(-

100

p)

in order

to

lacilitate

the reactions.

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is

usually

recommended that

operations

be

carried out

at a

tempe-

rature which is

sufficient to dissolve all carbonates but not too high

to

prevent

possible

oxida-

tion

of

the organic

matter

15,14,361

i.e. about

70'

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4/19

Sample,

IFP

No.

H/C*

o/c*

x

100)

Organic

S,/C*

(x

100)

N,/CX

(x

100)

Fe

(weight

9o)

C

(weight

vo)

C

recovery

(.qo)

Green

River

Shales,

USA,

Eocene

t5760

1

2

|.64

7.8

0.6

1.&

0.i

78.0

95.9

l

.55

8.1 0.4

I

.65

0.1

'76.0

Green

River

Shales,

USA,

Eocene

15190

1

2

1.16

3.3

1.7 2_5

1.9

75.1

101.4

1.12

3.6

0.9 2.1

t.l

77.8

Torbanite,

Australia,

Permian

15844

I

2

I .54

3.5

0.6 1.2

0

83. r

97.1

I

.53

3.7

0.6 1.1

0

80.8

Messel

Shales,

Germany,

Eocene

I

15132

2

I .39

21.'7

t.7

2.1

I.0

65.3

94.6

I .33

19.6

0.9 2.3

0.6

67.1

Lower

Toarcian

Shales,

France

1

10696

2

1.21

14.9

2.5 2.3

6.2

58.8

98.6

1.24

14.2

2.9

2.2

I

_2.

68. I

Siluro-Devonian

Shales,

Algeria

1 4085

I

2

0. Bl 5.0

0.7

3.8

8.2

66.9

101.8

0.74 8.6

2.3

3.8

0.8

10.3

Jurassic,

Mexico

25838

1

2

1.2'7 13"8

14.5 2.9

15.6

24.8

101.9

1.08

6.5

1.2

2.3

t0.7

53.1

Springhill

Shales,

Chile,

Jurassic

1 1463

1

2

0.60

t1.1

0

0.8

3l

.9 20_9

95

0.'/0

9.9 3"9

1.8

/1

50.7

Peat,

F{olland,

recent

1

5557

i

2

r.00

54.5 0.8 1.4

0 53.1


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6/19

In

the

end

the

attitude

towards

the

problem

of

mineral

impurities

in

the

kerogen

isolated

by

hemical

means

should

be

pragmatic:ii;;;.."

observed

at

IFp

thatstatisticaily

it

is

possi-

le

to

tolerate

a

pvrite

content

as

high

as

40vo

by

weight

"r;/;;;.;;tent

of

orher

minerals

as

igh

as 15vo

by

weight

(chapter

+i*lirr"ut

.xcessive

difficulties

io.

rur..

analyses.

Procedures

for

kerogen

isolation

a

Aromolic

C=C

mostly,bonded

qurnones,poionzed

woier

I

{-=O

I

CH2

+[H3

llJ'i'

Aromotic

C-H

(bendrnq-

-ou1-of-plone

)

1,,,

>4

I

I

Solu

roied

C-H

-ffio-Trffiiloo

1800

1600

1400

r2oo

rooo

eio

WAVENUIv,IBER

cm-r

Aromolic

C-H

* Absorplion

of f/uosrlico/es

b

--.------

bu0

3200

2800

1200

1000

800

Juvv

J.uu

zuuu

jB00

1600

l4O0

(

__WAVENUMBER

cm_r]

liiim,

til

lllln

,ilntf

lllir.lt

ltr iilii

lrl

illL

llr

,

, ri

rn

L

Fig.

2.1.a.

-

IR

spectra

of

a kerogen

sample

from

Mexico

(IFp

No

25g3g):

1.

Before.

2.

After

boiling

HCI

treatment,

showing

the

disappgarance

of

bsorption

bands

of

neofoimed

nuo.ijer.

Fig. 2.1.b.

-

IR

Spectrum

of

a

ralstonite

sample.


7/19

9'86

t-r

I

I

0l

LS'I

t.

z

I

auoJoa

'vsn

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to^rx ua:_.

t

s'0

0I

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z'16

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8'0

e

6V',l

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a

I

uenurod

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6',16

t._ I

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z

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urcrloptO'eruolsA,atrsl:\-

:.i

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r

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z

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ur

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L

t uortelosr

uaSo:a1

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8/19

Procedures

for

kerogen

isolation

3. Effects

of reagents

on

organic

matter.

Surveys

of this

question

have

been

made

by

Saxby

[33,

34,

351.

a.

HCI

and

HF.

HCI

and

to

a

lesser

extent

HF

have a

hydrolyzing effect

on the

oM

of

sediments. The

lesser

evolved

the

OM,

the

stronger

is

the

effect.

Reactions

other

than

hyclrolysis

are

possible

[33,

341

'

(According

to

the

erperience

acquired

at IFP,

the

addition

of

chlorine

and fluorine

is

probable)'

Oxidation

of

the

OM

can

be feared

if

the

temperature

is

too high (

>

70.

C),

espe-

cially

if

the

preparations

run

dry

[5,

14,36].

Therefore performing

the

attacks

under

an inert

atmosphere

is

advisable.

The

extent

of hydrolysis

can

be

evaluated

by

an

organic

carbon

balance.

Durand

et ot.

l10l

have

shown

that

for

a

series

of

coals

ihe

carbon

loss

was

about

l0

to

15%

at the

peat

stage

and

was negligible

beyond

the lignite

stage.

For

an

equal

degree

of

evolution,

this

carbon

loss

is

greater

for

so-called

"marine"

or

"lacustrine"

OM

(as

ofposed

to

so-called

,,continental,,

which

like

coal

is largely

derived

from

the

constituents

of higher

vegetation

and

especially

lignin)'

It

is

probable

that

this

figure

can in

certain

cases

exceed

50go

at

the

recent

sediment

stage

[1,

6, 18].

Measurements

made

at

IFP

indicate

however

that

for

ancient

sediments

the

carbon ioss

due

to hydrolysis during

the

preparation

of

the kerogen

is

generally

Iow.

Statistics

for

45

samples

of

very

varied

origin

show

an

average

carbon

loss

of

5.8g0.

Most

of

this

car-

bon loss

moreover

is

very

probably

due to

handling.

The

effect

of HCI

and

HF on

the

chemical

composition

can

be

studied

with

rock

which

is

very

rich in

oM.

Table

2.2.

shows

the results

of

elemental

analysis

made

before

and

after the

treatment

of

such

rock.

The

corresponding

OM represents

a

quite

broad

range

of

the

chemi-

cal

slructures

to

be found

in

kerogen.

with

theexception

of slightlyevolvedrocks,

elemental

analysis

are not

modified

to

a

great

extent.

This result

was

also

obiained

for

a

series

of

coals

[10]

'

However,

fixation

of Cl

and

F has

been

experienced

in

some

cases.

It

increases

with

evo-

lution

of

oM

due

to burial,

owing

probably

to

the

increase

of

microporosity

and

aromaticity,

and may

reach

several

percents

weight;

this

fixation

could

occur

by

absorption

of

HCI

and

HF

in the

microporosity

or by

addition

and

substitution

reactions.

other

methods

of

investigation

such

as

IR

spectroscopy,

dark-field

electron

microscopy

(EM),

electron

spin resonance

(ESR),

spectroscopy

and

thermogravimetry

do not

show

important

rnodifications

either

(tl0l

,

Fig.

2.2.).

once

again immature

oM is

the

rnosr

affect-

ed'

For

example

we

can

indicate

the

very

marked

increase

in the

lunction

C

:

O at I

700

cm

r

in the

IR

spectra

of

pear

and

lignite ([10],

Fig.

2.3.)

Since

all these

observations

were

macie

with

overall

study

methods,

it

is

obviously

not

pos-

sible

to

state

that

there

were

no

modifications

in

detail.

In

addition,

in

the

case

of

sediments

with

less

oM,

the

chemical

bonds

between

the

organic phase

and

the

mineral phase

wouid

necessarily

be destroyed"

The

effect

of hydrolysis

on

oM which

is

not

greatly

evolved

and

especially

on recent

sedi-

rnents

is

such

that

in this

case

the

term

kerogen

should

not

be

used

for

the

residue

of

acid

attack.

The

analytical

object

(the

residue

of the

attacks)

is very

different

here

from

the

initial

concept.

In

the

case

of

so-called

"marine"

or

"lacustrine"

OM

where

the

effect

is

greater,

a

large

part

of

the

organic

residue

of the

acid

attack

probably

consists

of

the

organic

fraction

which

is

not

contemporary

with

sedimentation

(reworked

products)

which

are

more

resistant


9/19

.

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eq

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r

ruJ

00/

I

reu

uorldlosq

sdnolS

o

=

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10/19

44

procedures

for

kerogen

isolation

2

ItiJil',lfli;.?:'n'

other

hand

for

ancient

sedimenrs

rhis

organic

residue

seems

to

be

very

It has

been

proposed

[17,

39]

to

use

acelic

acid

or

carbonic

acid

fbr

reducing

the possible

ffects

of

hydrochloric

acid.

The

first

has

the

disadvantage

of

being

an

organic

acid.

There

is

he

risk

that

it

will

not

be

possible

to

eliminatert

comptJtety

ur,.r',t.

attack.

The

second

isffective

only

at

high pressures.

In

anv

case

the

fact

that

it;;r;;;r;".y

ro

use

HF

for

the

des_

ruction

or

silicates

does

away

with

the improvement which

was

intended.

b.

Agents

for

destroying

pyrite.

Reducing

agents.

LiAlHo:

this

is

the

only.

reducing

agent

whose

..^fI".-,1

on

kerogen

have

been

systematica'y

tudied'

It

is

used

in

solution

in

tetralivdro

fuiran

[22,33],

or

di";;;;

mixed

with

diethyl

ether

EFFECT

oF

No3H

rREArMENldi. tli;'.NrAL

ANALysrs

oF

KER.GEN

(NO3H

40V0,70"

C)

l.

Before

NO,H

treatment

2.

After

NO,H

treatment

*

Atomic

rarios

I

'

L,

I

Sample,

IFp

No.

H/C*

o/c*

(x

100)

Organic

S,/C*

(x

100)

N,/C*

(x

100)

Fe

(weighr

vo)

C

(weight

vo)

C

(recoverl

vo)

Lignite,

Germany,

Eccene

I

15238

2

Green

River

Shales,

USA,

Eocene

I

15760

2

Green

River

Shales,

USA,

Eocene

I

15409

2

Lower

Toarcian,

Shales,

France

I

I

i

ro6e6

2l

0.'77

35.7

1.0

59.1

0.55

57.8

1.8

0.4

6.9

1.8

0.4

0.5

49.5

t.64

4.6

80.0

68.8

1.65

r

3.5

0.6

1.3

4.1

0.7

0.0

2.0

72.3

r .56

10.

I

72.4

61.9

1.48

21.9

0.5

7.5

0.2

6.2

65.2

L26

13. 1

3.1 2.'7

61.5

45.0

t.t9

35.5

2.0

8.2

0.2

57.0

uouala

Basrn,

cameroon,

Cretaceous

2

13356

2

Green

River

Shales,

USA,

Eocene

I

15789

(Heavy

fraction)

2

0.54

6.5

0.0

2.4

4.8

17.4

6l

.3

0.45

27.4

0.5

7.6

0.t

64.1

r.48

20.7

t+.J

0.0

36.0

7.8

1.01

))4

R-

Noz

3400 3000

2600

1800

1600

1400

1200

1000

800

4

I

Aromotrc

C=C

mosl1y,

bonded

qutnones,po

or zed

woler

c=o

I

cHr*cHr

I

I

l'i'

Soturoled

n-u

Aromolic

C-H

I

+

+WAVINUMBERcm-r


13/19

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polJad

e reue

onle^

Sullltull

eql qceor pue

('clo

'acr,rop

cruoserlln

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i

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,{1lecrlcerd

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14/19

O

COALS

^

UINTA

BASIN

r

TOARCIAN

FI

()l

=15

ilE

t

rl=

zlu

lrJl

Y

(rl(-)

olc)

rlE

9l-

=lH

l=

=l

,i

.:

Fig.

2.6.

-

Weight

ratio

of kerogen

extract

reflectance

for:

to

rock

extract

as

a function

of

vitrinite

o

Coals.

A

Uinta

Basin

series.

I

Lower

Toarcian

series (paris

Basin

and

Posidonien

Schiefer

from

Germany).

Kerogen

is

prepared

from

the

CHCI,

extracted

sediment,

then

extracted.

Fig,

2.7.

-

Gas

chromatograms

of

saturates

from:

l'

cHCl3

extract

of

the

sediment.

2.

cHcrr

ertracr

of

the

kerogen

prepared

from

the

cHC'ri

extracted

sediment.

Lower

Toarcian

sample

frJm

c".'.u,ry

(Posidonien

Schiefer,

IFp.

No

20508).

L

t

a

^-

--"---.,-.-1,...1-.'",,,,-..,,_r

l-,.,-,1"

r.1

.-

1,,

*l

AROI\4ATICS

"G"'

3a_)

2A

lr

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-',,",i,'i1

"

1

'

,

,,

l0

b

l

ll

';'-

'1

.

I

]I

rll

i-i

i',r,

,

17

"

1i1

A


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16/19

50

Procedures

for

kerogen isolation

2

vered will

be

richer

in minerals,

either

original

(physical

and chemical methods)

or

neoforma-

tions

(chemical

methods).

Petrographers

generally

prefer

physical

methods

to

chemical

methods.

Physical methods have

a tendency

to favor the recovery

of large-size

elements,

especially

microfossils,

organic debris

and

large

areas of macerals

which

are the

special

objects of study. Separation methods

by

centrifuging,

heavy

liquids

or flotation

(Chapters

3

and

12)

are

the most

frequently

used.

In

addition,

chemical methods

are

thought to modify

the optical

properties

which

are

used

for

analysis

and especially

for

fluorescence

(Chapter

12).

Among

petrographers,

palynologists

are

perhaps

the most

exigent

as

to the

preservation

of

the

morphology

since the ornementation

of

pollen

are

often

indispensable

for

the

determina-

tions. The

problem

of

grinding

is therefore

even

more important

for them.

They

prefer

che-

mical methods

to

physical

methods

since

they work

principally

with transmitted light

methods.

In this case

chemical

methods

make it

possible

to obtain

cleaner

preparations.

For

them,

pyrite,

because

of

its

opaqueness, is an obstacle

to

observation,

and they often elimi-

nate

it

by

nitric

acid

treatment

which obviously has

the

result

of making

the

recovered

frac-

tion of OM still

less

representative

of

the

whole

(cf.

paragr.II.B.3b).

This treatment

does not

change

the morphology

and has some

effect

on the

colors

(the preparation

becomes

brighter

or darker). Pyrite

and other residual minerals may

also be eliminated

by centrifuging.

It

is

probable

that the

contradictory

requirements

of

chemists,

petrographers

and

palyno-

logists

could

be

reconciled

by

means

of

a systematic

study which

would

define, more

closely

than

has

been done

up

to now, the

consequences

of

grinding

on morphology,

the

quality

of

extractions and chemical attacks

as

well

as

the

consequences

of

chemical

attacks on optical

properties.

A unification

of

operating

procedures

if

possible

would

greatly

facilitate

the

synthesis

of

petrographic, palynologic

and

geochemical

analysis

for

the

same samples.

IV.

OPERATING

PROCEDURE

USED

AT

IFP

Operating

procedures

are very

varied

in

spite of the fact that

there

are many

restrictive

con-

ditions. As

an example we

will

describe the

procedure

used aI

IFP.

This

procedure was

designed

for

physico-chemical

rather than

petrographic

analysis.

However many

petrographic

analysis with reflected

light

have

been made

with

kerogen

pre-

pared

in this way.

On the other hand

it

seems to

be

difficult

at the

present

time

to

use these

preparations

in

palynology,

mainly

because drying

and

grinding.

The

sediment

is first

ground

in

an Aurec ring

mill

for

30

s. In most

cases

the

grain-size

mode

produced

in

this way

is 80 to 100 p.

There is

then chloroform

extraction in

a

beaker

placed

on

a

magnetic

heating

agitator

cove-

red

with

a

cap

filled

with

water. The

operation lasts

for

an

hour

and

the temperature

of the

chloroform

is

around

50"

C.

The

extracted rock

is

then

collected

by

filtration

with

fiberglass

paper.

The rock

is then

placed

in

an apparatus

in which

acid attacks

and washings

are carried

out

followed

by filtration

with

an 0.6

p

filter

[9],

(Fig.

2.S).

All operations

take

place

between

60

and

70o

C

in

a

nitrogen

atmosphere

so as to avoid

possible

oxidation

of

the

kerogen

during

preparation.


17/19

splnu

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oqt

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J

.

59

1see1

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18/19

52

Procedures

for

kerogen

isolation

REFERENCES

are removed

from

the

reactor

by

means

of

a

peristaltic

pump.

The

proper

temperature

is

maintained

by

means

of

hot

water

circulation

inheating;uct.tt.

The

reactors

have

a

capacity

of

0'750

litre

and

are

made

of

a transparent

fluorinateJ

polyme..

The

maximum

amounts

of

rock

subjected

to

attack

are

about

50

g

for

highly

silicate

rock

and

100

to

200

g

ro.

u..f.u.-

bonate

rock.

The residue

of

the

acid

attacks

is

recovered

by

means

of

the

0.6

p

filter.

At

this

stage

an ali-

quot part

may

also

be

recovered

for

microscopic

study

and is preserved

in

acidulated

water.

Indeed

kerogens

are

more

difficult

to

study

under

the

microscope

if

they

have

been

dried.

There

is

no

extraction

from

the

residue

with

organic

solvents.

It

is

dried

in

a vacuum

at

100"

C

(80'

C for

slightly

evolved

oM).

Aliquot parts

for various

types

of

analysis

are

pla-

ced in

sealed

small

containers (l-10

ml).

It

has

been verified

that

they

can

be

preserved

in

these

containers

without

significant

alteration

by

means

of

elementary

analyses

carried

out

at

regular

intervals

on kerogen

which

has

been

frequently

handled

and

iherefore

exposed

to

the

light

and

air.

At

the

present

time

residual

minerals

are

not

eliminated.

Is has

been

observed

empirically

that

physico-chemical

analysis

were

generally

possible

if

the iron

content

was

under

1890

(corresponding

to

a

pyrite

content

of

around

40Voj

and/or

if

the

contents

for

minerals

other

than

pyrite

were

under

l5go.

Most

of the

physico-chemical

analysis

mentioned

in

this

study

were

carried

out

with

kero-

gen

prepared

in

this

way.

It

is

planned

to

make

the

method

for

eliminating pyrite

with

iron

sulfate

in

an

acid

medium

a

routine

operation.

For

this

purpose

the

acid

attack

residues

will

be

given

a treatment

for

twc

hours

with

a ferric

sulfate

solution

(150

g/1)

in

HCI 4i/.

only

the

kerogen

which,

accor-

ding

to

element

analysis

contains

iron

contents

of

more

than

1090

by

weight

will

be treated

in

this

way.

Under

this

value,

the

risk

of

oxidizing

the

kerogen

cancels

out the

advantage

of

working

on

cleaner

kerogen.

The

operation

is

followed

bytreatment

with

HCI

4.Vfor

t hr

and

then

by washings

in

order

to

eliminate

the

residual

iron

sulfate.

It

is

also

planned

to

retreat

the

kerogen

with

low

pyrite

contents

(Fe

< 10Vo

by weight)

but

which

is

rich

in

other residual

minerals (>

7-8Vo)

by hot

HCI

6l/ior

2

hrs

in

order

to

eiimi-

nate

possible

neoformed

fluorides.

All

this

can

been

made

in

the

apparatus

shown

on

Fig.

2.gby

replacing

water

by

polyethy_

leneglycol

in

the

heating

jackets,

which

makes

it

possible

to

increase

the

treatmentiempera-

ture up

to 95'

C.

It

is worthwhile

to note

that

this

apparatus

can

be

used

for

other

kinds

of

preparation:

It

is

for

example

well

suited

to

palynological

preparation

by modification

oi

tir.

procedure

(coarse

grinding,

no

stirring,

shorter

attack

times).

l.

Bordowskiy,

O.K.,

(1965),

Marine

Geotogy,

3,3.

2.

Burlingame,

A.L.,

Haug,

p.A.,

Schnoes,

H.K.

and

Simoneit,

B.R.,

(1969),

in:

Advonces

in

Organic

Geochemistry

1968,

p.A.

Schenck

and I.

Havenaar

ed.,

Pergamon

Press,

Oxford,

85.

3.

Combaz,

A.,

(1970),

C.R.A.S.

270D,2240.

4.

Dancy,

T.8.,

(1948),

ph.

D.

Thesis,

London

Uni_

versity.

5. Dancy,

T.E.

and

Giedroyc

V.,

(1950),

J.

Inst.

Petroleum,

36,

593.

6.

Debyser,

Y.,

Dastillung,

M.

and

Gadel,

F.,

(1977),

Proceedings

of

the

9th

International Meeting

of

Organic

Geochemistry,

Moscow,

1977.


19/19

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durand and nicaise 1980 - procedures for kerogen isolation

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