Asphaltene

Adsorption

Desorption

From

S.T.

SPE,

Dubey,

Shell

Development

and

Mineral

Co

, and

M.H.

Surfaces
SPE,

Waxman,

Consultant

S)% 1f+%?
Summary.

This

the effect
ability

paper

of adsorbed

of solvents

reports

results

asphaltenes
to remove

of asphaltene

on rock

adsorptiomfdesorption

wettabtity

asphaltene

from

aod

a screening

arid

formation

kaolin

on clay

minerals,

silica,

and

carbonates.

pyrolysis-flanw-ionization-detection
core

It afso

(1-FfD)

describes

test to evaluate

the

material.

Introduction

Reservoir

nettability

distribtuion,
tions

is a major

and flow

affect

formation

behavior,

of polar

ends

tions.
Nettability
ity those containing
of these

their

onto

and

Signhlant

factors

on mineral

surfaces
films

mineral

was

that conkol
are

mture

tents

of the cmdq

adsorption
surface;

(4) the presence

of colloidal

of the hydrocarbon

as resins,
The
afso

of the high
element

in

determinations
associate

1,650
(e,=
the

to

2,100

2.3).

These

molecuku
The

that
Vapor

compared

and

struc-

the

in crude

of various

solvents

volubility

parameters,

asphaltene

volubility

was

compared

ca bitumen

with

a series

of 40:

1) with

dition

of an excess

ed

asphaltenes

solvents
For
iation
toluene

The

vents

has

a 6 close

donor

of our

in hydrogen-bond

electric

constant

CoPyrighl

1991

and

may

between

separated

from

of

6 and

&
was

was chosen

Athabasratio
by ad-

to, the

finking

asphaltene

value

moment

of solvent
kaolin

because
required
Chloroform
other

14 hours

of Petroleum

Engine.,,

Adsorption

and kaolin

as the adsorbent.

1 gives

and

is predominantly

The

gas,

TabIe

analysis

(n-

clay minX-ray

in the so-

Bn+auer-Emmett-Telle~

was

11.9*0.4

capaci~,

m2/g

(five

measured

de-

by Ba/Mg

was 4.572
meq/100
g.
and toluen.
were analytical
reagent grade
contained
c 400 and 200 ppm water,
re-

99%

Fisher

pure

nitrobenmne

for

was

varex-

solcomplete

is a proton
higher
two

dried

titration.

(with

(&&r

<10

n-Dodeca.ne
ppm

Chemical

by storing

before

use.

and cooled

solvents.

over

Kaolin

water).

Co.)

0.4-mn

(Aldrich
Analytical

had

=300

ppm

solutions

molecuh

sieves

was

at 1 IOC

mineral

in a desiccator.

and ~Dhdtene
asphaltene

rnechsnicslly
rated

dried

Glassware

were

concentrations

di-

fo~48

tkom

Both
were

sofid

initial

for

was oven-dried;

manindated

Spectronic
were

under

C@ nitr-

marked

from

for

the

Asphaltene

concentration

Asphaltene

& Lomb

concentrations

curves,

of absorbance

except

nhrobenzene,

solutions

vs.

mn-

for which

appearance
vs.

the

titrated

a series

of straight

by these

lines

as practical

solubiliv
Adsorption

parameters

precipitate,

and

witi

lines.

ratio

The

the x-axis

Clays

and

migerals
.-

was

a
were
(mil-

(milliliters

cotangents
have

been

solvents.

Minerals.
also

at

determined

ratio

for the individual

on Other
clays

solvents

endpoints

n40decane/asphJtene

obliter-

n-dcdecane,

of solventlasphaltene

0, formed

were
with

respective

Titration

produced

on qther

compared
against

of a..phaltene
Plots

systems

and

in the

each

asphaltenes.

examination.

gram)

1I test

the angles,

adsorption

Sh&en

was sepa-

a Bausch

solvent/asphaltene

were
for

by the fist

gram)

liquid

solution
with

calibration

of the Bichard

precipitant

per

to 2,500

were

used.

by microscopic
liliters

asphaltene

MI for all solvents

concentrations

reference

300

centritigation.

6 values

vafues.

from

of 1:100

temperatures;

spectmphotometer.

by a variant

vsrious

at ambient

spectmphotometcically

at 450

mm was

varied

in the ratio

equilibrium

determined

ature

per

by

1001 m

Practical

were

solutions
hours

and

determined

AsphaRene
Sm{ety

oppolar

asphaltene

Elemental

the clay

N2

to Karl

was

were

fnitial

for

of ifs increas-

and bas a somewhat

Omn the

were

6 values,

Solution.

solvents

cation-exchange

48 hours

solvents

600

Complete

obtained

of aromaticliliphatic

sample.

formation
dipole

at least

centration

at 1.75 to 1.fs2 wthvt

primarily

mixture

From

Co.)

that

with

according

grade

tained

mineral

of their

a tar-sand-derived

of 15 % illite

area,

titration,
chloroform
Co.) and

of precipitat-

increasing

on the clay

indicate

consisting

Co.)

Kaofin

analysis.

conductimetiic
The solvents
@KUickmdt

be

Speight.

obtained

percent

toluene/n-dodecane

process

in core-cleaning

capabilities.

in different

DDm. Mineml/a?.Dhdtene

volume

the effect

To
as well

ogen atmosphe~e.

benzene

in terms
and

bitumen

experiments,

tolueneln-dodecane

solubilization

with
in the

of water,

desorption

on the basis

Chemica3

The

for
of

calA cm-3/2.

series

and chloroform

& The

linearly

asphahenes

adsorption

solvent

in

Mitchell

weight

on the
effectiveness

with

elemental

surface

Solvents

particles.

precipitate

The

Baker

terminations).

bond-

weighs

relation

out
sample

(XRD)

reagent

determi-

6,700

(solventlbimunen

asphaltene

adsorption

for asphaltene

smined.
ing

828.4

initial

by

of solvents

decreased

with
our

J.T.

Chemical

weights

expressed

& The

of n-pentane.

of tie

been

of asphaltenes

the maximum

solubilization

has

of adsorption.

the presence

their

on

carried

form,

@ET)

in the

osmometry

asphaltene

continued

the weight

hydrogen

molecular

individual

the kinetics

reduces

water.

is reflected

to

that the

surface

all systems.

hydrogen-bonding

asphaltene

dium

colloidal

asphaltenes

molecular

5,000

a wide
solution.

indicated

mineral

solvents
chosen

Adsorption

diffraction

solution.

pressure

nitrobenzene-derived
of the

that

were

with

toluene

Experimental

eral (from

con-

molecular-weight

and

produce

with

Hildebrand
They

and

insoluble)

these

intermolecvh

(6,=34.8)

weights

power

character,

pentane

and (5) the abifky

deduced

in dilute

association

weights.

in nitmbenzene

have

even

in asphaltene

molecular

nations

Solvents

stability

and resins

including

solvents,5

aggregates

et al. 6 showed

is involved

observed

measureinente,

in various

or form

Moschopedis
ing

erations,

spectively,

physici?l

to evaluate

were

procedures.

A varietyof

examined

out

from

on the

work,

from

of various

studies

aggregates
~, the oil or even to dissolve
them into true solution.
Fmther,
speafic
asphaltenehninerd
interactions
control
the degree
to which such adsorption
is irreversible
with respect
to various
organic solvents
and, hence, may determine
optimum
Iaboratow
corecleaning

excluded

effects

Asphaltene

and resin

to stabfize

was

for further

carried

and Cuiec9,10

of water

and can affecf

cases

and resins
and

1 Clement?s
iibn

also

absorbents

and

study.

thickness,

or ag~egates;

base

were

and clay

adsorption

establish

frac-

of asphaltenes

of the crude

asphaltene

studies

mineral

of a thin

in the

for

of asphaltenes

micelks

fraction

reversed

particularto adsorption

(3) asphaltene

and Melmse,

is found

(2) the chemical

substratq

CoUins

and resin

is a major

selected

(1) the presence,

of the minerti

oils in the form

minerals

of other

presence

of asphaltenes

adsorption

variety

The wetThe highest

1.4 Because

chzacter

therefore

on the mineral

tural

surfaces.

by specific

changes

of water

generslly

in the asphaltene

and multifunctional

adsorption

nettability

oils.

alterations
of oil-bearing
formations,
clay m@erds,
have been amibuted

weights

Asphaltene

permeability

maybe

in cmde

compounds

particularly

compounds

molecular
resins,

organic

of cmdes,

relative

surfaces

compounds

fluid
condi-

oil saturations.

mineral

organic

the location,
Wettabtity

and

and residual

water-wet

of polar

concentra,don
heavy

pressure

properdes,

of originally

by adsorption

controllkg

of the system.

capillary

electrical

tabiMy

factor

properties

of
used
Li, 12

Asphaltene

measured.

BET

ous solvents,
TABLE

1 ELEMENTAL

ANALYSIS

FOR

ASPHALTENES

P-FfD

the original

Amount

Element

(wt%)

Atomic

79.35

H/c

8.05

N/c

0,0097

~~ 9.2

SIG

0.0434

2.26

o/c

0.021

Ash

0.9

(Ni,w

0.24

1.21

100.0

sandstones

wet

plugs

areas

were

plete

adsorption

u+se,

adsorption

ppm)

were

atone

nnd

fnitial

Si@Im

equilibration

weight

of ~olution

known

weight

dure

was, removed

was terminated

were

fresh

effects

Atler

were
P-Fff3

pyrogrwm

the original
amount

until

the

was

lbt was carried

(1.75:

1.00

witi
tion

were

solvent

Initial

soIutioi.

used
was

washings

In some

The

Method

use of the P-FID

ciencies

in core-cleaning

methcd

measures

Details

of

Multiple

method

of

for rapid

operations

wM

The

experimentnf

samples

were

organic

method

subjected

TABLE

are

to extensive

Type

OF

coverage,

with

unique

effi-

vent

P-FfD

with

13

Asphaltenes

Per

was

solubfity

(Ca,vt

-?J2)

foflowed

monolayer
isotherm
mg/g,

adsorption.
plateaus)

toluene,

equation

ma

to 2.5

was

FROM

adsorption

levels
not
Type

of the adsorbed
with

NONPOLAR

at

of the adsorpin good

studies

from

and

in sever-

Gif10tt3

of solvent

on monmoflonite

Mineral

obtained.
I isotherm

plateaus,

asphaltene

monolayer

a decrease

in

the weight

6 from

Unit

Surface

Monolayer

Area

Thickness
(rim)

25.8..

2.0

1.757

Toluene

3.9

26.4

26.2

2.2

1.9

2.7

Toluene/

8.7

29.8

30.1

2.5

2.2

3.0

n.dodecane

.Yxlculeted

Wuwt)

Calc!a!ed
* Awmms.0

1,,.1.

ply

mm

Ihnw

from

uncorrected

edge

transform

sdsrptbn

BEl
Wth

0+ L.a.wnulr

Isotherm,

$fia.~

area

planar

wfaee

of 11,9
ares.

Ok.

(clas)

increased
9.3

SOLVENTS

(mglm)

(mg/g)

+ (n@).

KIzlg desi@i d mphaltaes=

; ,145 glcma
0,9 d fold surface arm also, whalt.ne

packing

fraction.

0,8.

but

with 30l-

23.8

isotherm

described

carriers,

Level
Per

agreevarious

montmorifkmite

Asphaltene

Unit

con-

~omplete

2).

Czamecka

Lnngmuir
mglm2

constants

the irdlucnce

parameters

asphaltene

are generally

conditiom,

observed

with
adsorption

9.3

. From

and

is

Chloroform

(1 ,75:1.0

Max-

decreased

respectively.

of rate

asphaltene

Weight
of

8 = 8.7

adsorption

(Table

of adsorption

per unit surface

KAOLIN

of

asphaltene

us values

the adsorbent.

Both

from

ON

limit

onfy

iu a va-

in qydlibrium

near-anhydrous

correlation

2.0

cot

solubilized

vs. equi-

K=rati~

values

As obtained
from

vari-

cm-3/2)=0.75

asphaltenes

asphaltene

wd

repotted

work.

pamm-

to Hfldebcand

lower

Langmuir

aS =saturated

plateau

under

volubility

toluenelndodecane,

of the

reactions.

Clementz2

Bic~rd

asphaltenes

23.8

d.$orpdon

monolayer
ment

2 leeO*

. . . . . . . . . . . . . . . . . . . . .. . . . . . ...(1)

ticmldesorption

simifar

elsewhere.

order
and

transform

C,

Adsorption

Solvent

Bent-

asphaltene

tolueneln-dodecane

for the

(at the

26.4,

a= asphaltene

Ma%imum

6
.~~

Cores

For tie

as adsorbed

indicadng

6 in the

centration

extrac-

at the

solvents,

adsorption
.8,

lineaf

Table

3(c2fh

isotherms

1 iiotlefms,

increasing

where

conducted

Tbe

extraction

2Adsorption

to 2
cores

in the effluent.

are completely

mineral

cla=(cl17J+(11a&),

on kao-

in t&e sample.

described

The

Practicaf

e.,

mixture

nonpolar

aspbaftene

The

adsorp-

of solvent

material

24 hours.

concentration.

the th~e

chloroform-29

Cleanfitress

evaluation

24

cores

are propotionaf

asphaltenes

adsorption

imum

procedure.;

was also examined.

the pyrolyzable

the

Core

houfs.

for

evacoated

and

solute.

series

solventsi.

on kaolin

solvents

Evaluation

these

asphaltene

ScIhItfOn.

asphaltene

1 shows

Langmuir

obtained.

for

550C

the resulting

toluene,

solvent

of solvents

For

adsorbate

washing

From

that these

al ion forms
P.FID

water-

tempsramre.

mzlg),

Mines

et al. 14 Higfdy

was visible

at ambient

cblorofonn,

with

for
Note

librium
of

was obtained

were

solvenb

Fig.
rie~

samples,

Soxhlet~

the multiple

at

of

mglm2.

in the toluene/n-dodecane
@J% .cm3n
(f?=57.

samples

solute.

for

cot 0, for this

& vafues

by P-FfD.

%phaltene

cases,

0.74

Adsorption
results

0+8.6.

intoluene/ndodecane

Subsequent

to check

Discussion

as the

adsorption

and ,the remaining

methods.

and

eters,

with

on irreversible

manner.

Results

mixtore

washed

The

by kaolin

washings

in a sbnik

was

titration

used

traces

and examined

adsorbed

an

and Bent-

Bureau

fo~ abo~t

2rea=0.49

level

Asphaltene
of

proce-

repeatedly

and the asphaltene

irreversibly

were

agreement

GET

asphzkene/

negligible

for the kaolinhphaltene

by P-FfD

sand

with toluene

showed

(blank),

of solvents,

methods

good

samples

toluene

obtained

mineral

wthvt)

beim

with

The

at various

out with 3,000-ppmaspbaftme

a variety

determined

examined

equilibrium

were

examined

and dried

aSph21tinelt01uene

at 110eC

of asphaltenes

evacuated

a known

step.

vacuum-dried

kaolin

IO@ no color

then

ratio

spectrophotometrically.

from these data.

The effect of differmt
tion

were

reicfdng

as determined

subsequently

toluene-ffushed

diluted

desorption

solutio~

adsorption

on &r&?

U.S.

by exuosing

were

were

the remainder

equilibrium

the kaofin

toluene

asphaltenes,

and

the next

in toluenc

surface

the

heating

made

were

a 2,545-

a kaolinlsolution
procedures

by

was

other-

obtained

equilibration,

giving

Solvents.

out with

After

obtained

treatment

(2,500

ppm.

concentradons,

with

were

carried

analytical

the final

-160

adso~ion

solvent.

solvent

for

when

was

Irreversible

and

and

Vafious

loop
was

measurements.

of toluene

concentration
reference

hysteresis

equilibration
solution

as in the adsorption

With

remain-

extractions,

by Donaldson

a.sphaftene

coverages.
Kaolin

developed

by

wt%

mineral$

concentration

from

amounts

asphaltenes

measured

Com-

or krypton.

for mog

asphaltene

From

isotherm

nitrogen

obtained

high

of kphaftenes

asphalteneltoluene

1:100.

either

as monolayer

solvent,

ppm

were

levels

desqtion

toluene

with

isotherms

ttien

Desorption
A

measured

of adsorbed

was

method

Asphaltene
. ....
surface

hydrocarbon

the various

at 110C.

pyrogm.m$

efficiency.

on nettability

(USBM)
Total

after

witi

Determination

effwt

hebn

of the samples

and compared

to evaluate

surfaces

of cleming

Nettability
The

obtained

material

mineraf

es-&ate

by vaiuum-dryiig

were

core

ing on tie

Ratio

,H
,~,.

,..

followed

pyromm

2,4*

to

8.7

!
~

-80

30-

1
;

24

-60

z
:

20-

3
.
~

-40

16-

:
s

12

Q TOLUENE/-DODECANE

!1.,5.1.0

WIW)

:
0

TOLUENE

CHLOROFORM

- 20
:
$4
>
.
;
,~
c
z

400

800

Fig.

of

1.145

from

g/cm3,

1.75

the

to 2,2
older

Afthough

nuclear

aromatic

chains,

asphaltenes

daf

iri flat

in solution

disks.
On

the

modeled
rated

these

of XRD

as disk-like

to 3.7 nm.

ious

consisting

afiphatic

sume

that

with
surface

face

area

the planar
area

disks

assumptions,

from

2.4

(an

6 to 8) with

gregates

the

increases

solvent

carrier

These
tmminations

asphaltene

Athabasca
oxygen

bonyl,

and suffoxide

in the

p~sence

they

are

micelles.
to the

with

part
These

solubdization

solvents

of thk

structures.

-OH

The major
and

6,19 Hydrogen

bonding

may

also

>

:
3
.

20

R
i
c

,5

i
:
F

,0

BEREA

DICKITE

SANDSTONE

Alter-

c-109

MESHI

[WISCONSIN]

DOLOMITE

OTTAWA

SAND

CALU7E

[DOVER

KAOLIN

m ILLITE

[DOLOCRON1
[SUPER

r-

.32s

MESH:

CHALKI

MINERAL
[BEAVERS

8ENOI

disks
ag-

a change

0
5,

in
de-

aggregates
0

1000

la in isolating

EQUILIBRIUM

resinous

ma-

Fig.

as hydroxyl,

car-

faces

of these

small

with

present

25

mixture.

daltons)

intennolecufar

groups

:
~

2000

ASPHALTENE

CONCENTRATION,

PDrn

20 to 21 % of the

such

contdfing

of the solvent

et al.,
that

$/

from

asphaltene

with

increase

molecula

in bitumen

involves
N-f

With

molecular-weight

molecufes

factor

solvents.

adsorbed
0.8.

asphaltenes

polarlpolarizable

solvents

the

parameter.

equilibrium

of asphaltenes

study,

egation in nonpolar
between

The presence

that
sur-

of lameflae

of the

found
1,200

faces

clay

of the asphaltene

form

groups,

in dynamic

smd

disk

further,

by the nature

(=

different

30
$

each

and var,
1 we as-

the

that

number

of n-pmtane-precipitated
.of and

with

rings

thicknesses

Fmkmam

functiomf

groups.

and

various

bhumen,

is Iow-molecular-weight
containing

urn,

to the toluenelndodecane

consistent

concentration,

from

sepa-

of the totaf

to 14,600

is influenced

the

bitumen

11,700

association

and

of lamellae

particles;
0,9

weight

that asphaltenes

this

of 2.2

with

diameter

that suggest

that

teriaf

about

from

therange

and Melrose,

volubility

molecular

chforofonn

are

and

asphakenes

from

tlom

results

solvent

that the average

apparent

of approximately

in the

ag.

are

monolayer

increase

decreasing

assuming

= 3 mn,

corrected

kaolin

35

without

clusters

aromatic

area)

density

flat

16

asphaltene

adsorbed

surface

side

nm,

to 0.38

is about

ppm

280:

as colloi-

thin

of the clay

a packing
the

to 3.0

mtively,

edge

have

these

faces

aliphatic

or very

Coflins
are

of the clay

(excludlng

asphalene

about

Following

2400

spheroids

polynuclear

aggregates

on

40

poly-

large

15

diameters
of 0.36

asphaltenes

as large
more

of a number

distance

of condensed

sidechains.

in contact

15.17 the
with

some

0,7x
flat

is composed

asphaltene

the planar

ve~

ASPHALTENES,

increase~

comprising

of

are

structures

An aggregate

with

presented

shape

studies,

by an interfamellar

Lamella

and

dimemions

whether
basis

sheets

OF

2000

sequence.

asphaltenes

are being

size

typicaf

discrimimting

ing

systems

for

thi&ess

solvent

15 represents

in

with

same

1600

C0NCENT8&T10N

isotherms

monolayer

the

literature

polydispersions

gregates

is

over

EQUILIBRIUM

IAdsorption

uncorrected

nm

1200

2Adsorption
from

that

for

adsorption

the

asphaltene

Asphaltenes

must

contribute

distinct

or in the

nonpolz

asphaltene
hydrogen

be a major

asphaltenes

on

clay

and

mineral

sw

molecules
means

in the

of

to[uene.

aggrbond.

cm-

infrared
1 regions

SiOSi
cant

of

a.sphaftenes

precipitated

adsorptions
owing

groups.

to the

adsorptionmechanism,

solvents

for the

mechanism

cleaning

operations.

sifica

stretching

asphaltene

to 3600

it cmdd

clay
and

vibrations

if hydrogen

desorption

and

of clay minerals

in the 370g

12 However,

asphaltene

on

in tie presence

influence
process

minerals.
have

1100

shmm
to 1000

of Si -OH

bonding
selection
and

and

is a signifiof efficient

eventual

core-

TABLE

3ADSORPTION
ANO

OF

MINERALS

ASPHALTENES
FROM

ON

TOLIJENE

VARIOUS

Asphaltene

Surface

Illite

Bend,

OK)

Kaotin

(Beavers
mineral

(J.T.

Baker)

Calcite

(Dover

chalk)

Ottawa

sand

Dolomite

(Super

X)

(Wisconsin)

Berea

sandstone

Alumina

(Type

(>

100

A, Fisher

TASLE

5.s

3.4
2,2

1.69

3.70

2.67

3.75

1.3

0.66

1,64

2.1

1.52

1.0

4-ADSORPTION
ANO

(Based

on

19.2

15.9

OF

MINERALS

adsorption

2.2

1.71

1.48

mesh)
Scientific)

ASPHALTENES
FROM

from

VARIOUS

Alumina

(Type

Calcite

(Omya

solution,

Kaolinite

Assumed

dry

20.8

2.0
0.s9
0,24

in Ref. 13 are
Wlh

incarwt.

buffered

sndl.m

of our data

for asphaltene
CoLiis

of 19.3

and

dlt Monlte

with

data

of Collins

adsorption

and

Melrose

18.0

m2/g.

used

kaolinite

with

&p

vzakes

bracket

mmresults

levels

of the higher

surface

areas

water

on
sur-

I isotherms

.tisogtion

were

been

isotherm,

Langmuir

2i@ku!dY

dine

of asphaltenes

on kaolin

1). Amhdtme

for &obeoz~ne

than

layer

coverage

is complete

=5.5

mglmz,

amounting

how-

samples,

adsorp-

lower,

1.55

and

indicating

asphaltene

from

for tb~ nonpolar

solvent

of about
layer

series.

65 mg/g

fniti~

kaolin

thickness

or

of about

adsorption
Asphaltene

run.
Evidence

creasing

of at least
rnolecuku

a pwtial

dissociation

degree

of ionization

(greater

mmberofp

as well

as in-

tained

for

Type

tion,

were

data

are

observed

clay

times

this

solution.

Ffg.

loading

asphaltene

i.e.,

,00

,500

!0,0
,$,ALT..,

,.lL,,.,,.

2500

20..

.mcwm,,,m,

step.

toluene

sobxion

kaotin

3-Adsor~iorddesorp
from

tcduene.

fion

hysteresis

ob3).

adsorp
the. lowest

thuringite,

adsorbed

about

3.7

and

mg/g

fmm

to the

process

usual

hysteresis

equilibri-

ppm.
relation

surfaces,

of the

pressure

sorption

decreased

hysteresis

on solid
the desorption

partial

in toluene
branches.

decreasein

to 160

to th+ left

loading,
that

with

2,310

adsorption

equilibrating

A desorption

desorption

in the deso@ion

to 16.6

is displaced

We suggest

Surfaces.

for the asphaltenes

where

adsorption
partial

required

the
patlu

pressure
for

the

ad-

for the asphaltene

,,,-

for

asphaltenes

on

on kaolin
the

average

reflects

the asphaltene

number

of lamellae

concentrating
of the

de-

asphaltene

on

micelle
(and

392

were

Adsorption
bad

however,

Kaolin

is opposite

adsorbate

the

sorption
pendence

Fig.

on kaolii

path

branch

tian

absorbents.

adsorption

concentration

at constant

is less

the

for gas and vapor

desorption

posi-

(3%ble

monolayer

Fe + + content,

on kaolin

of 26.0

hysteresis

observed

solution

4. Chlorite

mg/m2;

From

obtained

3 shows

a maximum

This

hig3

of Asphaltenes

Asphaltene

0.24

these

themselves.

substrates

mineral

3 and

groups

Additional

of asphaltenes.

was also

um

all Omse

with

amount

Desorption

2), indicadng

level,

surface.

toluene

(Fig.

oxy-

of preferential
nitrogen

between

mineral

in Tables

minemf

isotherm

from

with

from

posi-

acidic

molecules

common

I isotherms

adsorption

chlorite

isotienns
and

summarized

asphaltene
,0

cIay

consists

to attraction

3%

condensed-ring

asphalrenic

on the clay mineral

owing

for

involving

asphaltene

on the asphaltene

adsorption
other

Lmgmuir

articles)of

follow
charges

the

charged

sites

S/cm

charged

step probably

positively

would

and negative

in

conduc-

respectively.
20
for mukilayer

solution,

aod negatively

has
found

and pyi.

toluenee.g.,

2..5 x 10-6

titrobenzene

present

charged

and

and

adsorption

between

and negatively
tive

botk

21 They

and mitio6.mzene,
ionic
mechanism

oitmgenous

The initial

interaction

x10-6

of solvents

in nitrobwem

in benzene

from

basic

groups,

shucture.

nitmbenzene

medwsiztiGwfiv

0.04

adsorption

charged

genated

multilayer

about

constant

and Speight.

COnduCt2nCZs

those

bmces

is obtained

at a level

SpE&C

with

dielectric

and Penzes

a.spbaftene
solution
in benzene
This
suggesk
a predominantly

mglg);

Aotionlevels

to an adsorbed

higher

compared
of

increasing

(26.4

of their

Il,

with

by Eldib20

of 30 and 20 mglg,

considerably
Type

solute

described

tively

(Fix,

higher

Wuhed.

asphaltene

and Mehosel

two

maximum

were

and

solution

with

basis

.X(dm

toluene

These

area

imn

from

Iangmuir

adso@ion

to remove

mg[m2.

Adifferent

4.8

i .7

10.5

0.73

asurface

.solution

1.5

21.3

a.i3

also obtained
respectively.
because
ever,
1,11

174.7

12.3

3.0

kaolinite.

tionson

Area.

(mg/m2)

9.1

o~y

face arias

Monolayer
Weightk3urfaoe

Chlorite

comparison

possible

Asphaltene

Thuringite+

.Valuea

Direct

ppm)

(mglg)

114

Scientific)

UF)

(Twiggs)

. . LeaChad

is

Carb

2,500

WeighUWeight

(mZ/g)

B, Fisher

CLAYS

SOLUTION

a.sphalteneltoluene

Area
Adsorbent

1.2

ON

TOLUENE

Surface

Mineral

1.1

26.2

11.9

Area

(mgfm2]

39.2

(Dolocron)

Oickite

Weight/Surface

(mglg)

(mzlg)

Adsorbent

Monolayer

WeightJWeight

Area
Mineral

CLAYS

SOLUTION

in solution.
determines

This
the

solution

size. and

is, in turn,

weight

3PE

of)

Zeservoir

tie

in equilibrium
adsorbed

Engineering,.

with

asphaltene
A.gust

1991

TABLE

5IRREVERSIBLE

ADSORPTION

OF

ASPHALTENES

ON

Concentration
in

of

Toluene

Level

Solution

on

By

593

26.8

1,381

26.3

2,160

26.1

ab$nrbmm
P.F[D

25.9

Afler

Asphaltene
Retained
After

Washing

(%)

49.0

method,

methad,

TABLE

6IRREVERSIBLE

REPEATED

ADSORPTION

WASHINGS

WITH

OF

VARIOUS

ASPHALTENES

SOLVENTS

OR

ON

KAOLIN

SOXHLET

(~a,

Solvent

h .~m

11

Tolueneln-dodecane
(1 .75:1

.0,

-312)

AFTER

EXTRACTIONS

Final

Initial

Adsorption

Adsorption

Freon

Toluene

(mg/g).

17.1

46
375

TOLUENE

Washing

Kaolin

(mglg)+

(ppm)

. .Zy

Level
Prolonged

Adsorption

Asphaltenes

FROM

Adsorption

Irreversible
Equilibrium

Equilibrium

KAOLIN

Asphaltenes
Retained
(%)

(mglg)

(mglg)
~

-1oo

7.6

30.7

8.7

30.8

3,9

30.s

25,5

62.6

29.2

24,6

S4.2

30.6

13.3

59.8

30.7

17.9

56.3

Wtlwf)

To)uene

Chloroform

9,2

52.9

16.2
Chloroform/acetone
(70/30

9.4

30,0

8.2

27.3

9.8

30,s

21.4

69.5

29.9

22,1

73.9

21.2

70.9

Vollvol)

Methylene

chloride

Chloroform/methanol
(87/13

10.5

30,6

16,2

52,9

10.6

30.6

6.7

21.9

4.1

13.5

30.3

2.4

7.9

32.8

1.6

4.9.

32.8

1.0

3.0

VOl/VOl)

Pyridine

10.9

Chloroformlmethanol
azeotrope
(76.7/21.3

VOi/VOl)

11.1

f.litrobenzene

11.5

Chloroform/methanol
(70/30

30.6

=18
21.5

72.1

30.8

6.9

22.4

11.2

37.3.

22.3

71.9

30.0

Vollvo[)

13.7

To[uenelmethanol

58.4

29.8

.,

31.7

3ze0tr0p0
(29.1

/70.9

VOUVOI)

. m&ePeae18~8:l$9s.
Now

Initial

adswplim

on 811 kaolin

PPm)

from

mm

3,000

samples

asphaltene

TABLE

@inept

solution

chlomfom

&d

chlomfmmlmethanol

In tol.enelndodecane

7SOLVENT

[1.75

CLEANING
P-FID

OF

:1,0

SILICEOUS

SCREENING

Solvent

<400C

27,000

CORE

MATERIAL,

Hydrocarbons
P-FID

400

to

(wt%)
7509C

Tbtal
0.624

~-

Hydrocarbon
Removed
by Extraction
(@~)

None

0.525

Pyridine

0.038

0.008

0.046

92.6

Tetrachloroethy16ne

0.050

0.023

0.073

8S.3

(Step

1) Toluene

0.013

0.022

0.035

94.4

(Step

2)

0.002

0.002

0.004

99.4

0.0s

0.02

0.!0

84.0

Chloroformlmethano[

azeotrope
(Step

1)

Methylene

chloride

(Step

2)

Chloroform/methanol

3ze0trope
(Step

1)

Chloroform

(Step

2)

Chloroform/methanol

azeOtrODe

Chloroform/methanol

3PE

VOI from

METHOD

Pyrolyzable
by

@ 87/13

wvwi).

meotrope

1991

0.001

0.001

0.002

99.7

0.002

0.006

0.008

98.7

0.004

0.003

0.007

0.004

0.003

0.007

96.9

,.

9s.9

393

TABLE

8USBM

BEREA

NETTABILITY

AND

BENTHEIM

USBM
Treatment

Berea

550eC

Adsorbed

aggregates

on

io the solvent,

as well

asphaltene

increasing

imum

value.

concentration

Thus,

must reattain
equilibrium
pared with the eriginul
composed
used

of fewer

in the

The

prucess

was

tractions

used

asphaltene

solvent.
cross
y axis

suggwts

tendency

01igiWdbJ

cores

by a number

of workers.22

ty of toluene

to remove

water

in tolucne

increases

with

au increase

mitting

direct

contact

(2) toluenes

from

to solvate

substrate

Clementz,2
on the basis
ties of tohmw,
6 shows

adsorbed
and

metbylene

dielectric

chloride,

predominantly

solvents,

~eotropc,

which

strong

and

und

,witb

bonding

of the

adsorbed

removal

capabilities
solvents

consist

simifar

so no selectivity

to

acceptor.

probably

reguired

the monolay-

largely

of hydrogcn-

pymgra.m

in asphaltene

molecufar

mechunism

on kaolin

of the adsorption

known

to be affected

To obtain

suitable

various

are taken

by the

core

special

ternatively,

cores

wettabifity

material

precautions

to preserve

the

4.

A high

degree

from

most

The

azeotmpes,

.ti the presence

perature

and

pressure

during

mineral

umdyses,

coring

and

wettabilky

to a water-wet

of reservoir
condbions

of the

cmde
(restored

one
after

state).

cores

oif-wet

than

adsorption,

on kaolin

decreased

min-

The weight
to some

pardcula

ulso

clay

conditions.

tolnene

from

extent

solvent.

solution
yielded

nitrobeuzene

indicating

with

followed

on other

clays

Langmuir

T~e

on ka.oliu

followed

voir

responsible

adsorption
to many

solvents

were

by pyridiw

Iornc

for tbe ad-

was

observed

solvents,

for

according

to

tbe cbloroformJmetbanol

toluene

azeotrope
98.9

sample.
by ~e

factors

adsorption.

was

particularly

ineffec-

removal.

removing

core

mukilayer

respect

5. Cldoroformlmetbanol
gle solvent,

Duaf

W%

was

the

of the crude

solvent

extraction,

ctdorofonnlmethanol

most

effective

oil in a siliceous
metbylene

azcotrope,

was

sim
~ser-

chloride
marginally

eff=tive.

6. Asphaltene
in a partially

treatment
water-wet

wettubtiity

of water-wet
or nmtrul

indices

sandstone

water-wet

cores

system,

und o&saturation-vs.

ravulted

as shown

by

-capiIk3ry-number

curves.
Nomenclature

a = asphaltene
as

adsorption,

satmated

adsorption

coverage,

concentration,

at compkte

mglg

ppm
index,

of rate

qtio

mglg

asphaltene

I = wettabilily

oc-

dimensionless

constants

of adsorptionldesorption

reactions
solubrby
~Om@t,

pununeter,
dimen~iO~es~

ca3~.

cm 3/2

ure

swfaces.
approach
the cores

condition,

condhion,
und brine

from

substrates

effective

in asphaltene

nonpo-

ama.lyses

the

of irreversible

P-FfD.

pure

weights

core

does
treat-

produced

more

monolayer

unbydmus
of

f3 isotherm,

on kaolin

sofids

for

speciul

for these

native-state

are clwmed

by aging

Maiy

ofl-wet,

monolayer

adsorption

Type

6 = Hidebraud
~r = &Je~ic
by P-FfD.

of about

Quilon-C~

asphaltenes

under

adsmpkm

asphaltenes

solvents.
Efficiency

to come-

of sandstones

(i.e.,

indicating

mechanisms
are probably
fbe major
sorption
mechanism
in nhmbenzene.

USBM
fol-

asphakenelkaolin

the

rock

by

a comela-

for a group

state,

= 0.4

power

minerul

3. Asphaltene

more

because

solvents

monolayer

for uII solvent-washed

of

I isotlenns,

solvent

Iamellae.
were

oil-wet

of the adsorbed

a Langmuh

of

Solvents

nonpolar

Asphaltene

as both
because

asphakenes,

Type

common

followed

of 85.6%.
are

asphaltenes

2.

chosen

was the cbforoformlmetbanol

average

nonpolar

and disper-

as a proton

content

to make

I vafues

attempt
found

treatment

for the adsorptionof

increasing

and

polari-

were

chosen

9 in his

made

asphaltenes

cores).

obtained

with

tive

of its high

capaboities

was

of

toluem

of low

iouizudon

its capability

of adsorbed

like

mixtyres

6Y otberszs

USBM

were
with

Conclusions

by

proper-

because

used

gave

wettabiIiU
tiand Bentheim

isotherms.

removal

used,

them

margi-

ace typical of waterthem to less water-

wettabdi~,

asphaltene

chlo-

was

removal).

treated

Cuiec,

and asphaltene

to a completely

resin

advanced

in the

solvents

and pyridine

96%

above

Extraction

394

mineral;

solvation

on the basis

hydrogen

removed

pyrogmms

as part

was
and

for inducing

efficient

from

asphaltene,

uses

dry

asphaltene

was chosen

the most

asphaltene

described

lm

high

constant

rernowd

adsorbed

The

selected

hydrogen-bonding

for effedive

curred

were

acceptors,

by pyridine,

P-FtD

of solvents

kaofin,

and potentiid

and

dielectric

bonded

g water/100

25 to 90 C), thus per-

Cbforofonnlmctha.nol

Of these

with

to 0.38

so[ubifity

wettabtity

cores

with

not

mcnt,24

methylene

observations

A3s0,

oil interactions
Although

that

oil

was

of the. cmde

azeotrope,

Siur

oils.

wt%

8 gives the USBM

and -entreated
Berea

on Berea

crude

and thickness

from

conclusion

systems.

20 reservoirs.

eral from

0.05

of water

Nhrobenzcne

for their

donors

lowed

described
of

with

different

after

98.9

extraction,

cmde

Table

IvfarchmB

rocklcmde

were

by (1) the abili-

solution

and

1. bngmuir

to comrefi

(solubili&

disperse

effectiveness

6 vafues.

constant

its high

and

the

surfaces

similar

from

mechanisms,

proton

er

the

asphaltenes

ties and high

sion

about

in temperature

W%

reser-

azeotrope

The I values for the untreuted

sands
the asphaltene
treatment
convened

asphaltene-treated

in tbe cmde ofi and to facilitate

their adsorption
m the
surfaces:
@
(3) the inabifity
of toluene
to reverse
the
process
sigmficantiy,
at least on a representative
clay

mineral

Table

mineral

(99.7

or neutral-wet

Crocker

14 mg/g.

been

has

effective

Wettabifi@
Tests.
for asphdtene-tmated

I,

removing

solvent

uOr-

3) must

intersect

than

can be expluined

from

of the tolueneloil

abfity

ag~egat~
dw fi~e~
adsorpuon

(Fig.

procedure
states

of

to toluene

and

greater

oiI-wet

Ths
water

toluene

isotherm

ex-

83%

respect

cuive

extraction

toward

in Dean-Stark

with

somewhat

ut?er

5. Toluene

On averuge,

adsorption

of the Dean-Stark

water-wet

iu Table

used

the desorption

loading

even

Dual

tool

smaff

of a sundstone

cbtorofo~medmnol

solvent,

sumple.

sol-

miner-

screeuinS

reauires

on the cleaning

by the cfdoroformfmethanol

tion between

by a considerable

as shown

udsorbed

of the

more

fmm

solutions

on kaolin,

det~ination.s.

dmt

portion

at an asphaltene

The

complicated

it is commonfy

irreversibly

nally

material.

>e

single

core

followed

dices,

solvents

that

with

water-wet

inexpensive

efflciencv

results

concerned

a stmangly

is a rapid,

core

effective

in the

wet

method

P-FfD

by different

sandstones
wet system,

max-

aggregates

concentrutod

adsorption

7 gives

procedure

to provide

extraction

of disaggregate

ride

late

toluene,

saturation

initiul

the more.

is funber

because

was

This
the

than

with

for core

to some

in a more dilute solution

comstep or with asphaltene
CIIMWS

asphaltene

extraction

soIvent

solvent

the presorbed

solvent

USBM

measurements.

of irreversible

prolonged

the

lamelfae

given

step,

withlfmse
adsogxion

adsorption

desorption

degree

in

in the desorption

tbe P-FfD

oil

with

restored-state

of the cores

A sorface,

the inost

increasing

of the

to evaluate

voir

+ 0.4s
+0.51

species,

part

extraction

Table

+ 0.90

as the solvent

vent

tions

Sands

Bentheim

kaolin surface.
The average
number
of lamellae
aggregate
is a function
of the asphaltene
concen-

the

in the asphaltene
tration

+ 0.97
+ 0.99
+0.12

asphaltenes

Index,

Sands

._

Heated,

fu the

TESTS,

SANDSTONES

Al-

followed

at in-situ

tem-

Acknowledgments

We

acknowledge

permission
chemical
for
tieir

the

the

to publish
Services
centrifuge

management
this

Gronp

of Shell

paper.

We

for P-FfD

experiments.

We

ujso

Development
acknowl@ge

measurements
dso

thank

Co.
the

and J.A.
the

for
Geo-

Roban

reviewers

for

August

1991

comments
SPi3 Reservoir

Engineering,

References
1. CoUin.s.

S.H.

and

on Reservoir
SPE
,..

,.

2.

Sydposium
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Clememz.

Complexes

CWy

Minemk

Fritschy,

0,

ponents

and

5.

Wihcrspo.n,
of

Minerals

and

Gillott,

and

28,

Papixer,

Model

.$hdla

June

senior

With

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312-19.

and

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Athabasca

Oil

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ford,

(1978)

57,

R. S.:

The

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a Bitumen,

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been

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Co.

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Ends:

The

Implications
1982

Aprit

4-7.

55,

of

Calgaty,

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Oil

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Jmeractions
and Weftabiiiy:
.kn Atfempt
To Understand Their Interrelation,
paper 13211 presented at the 1984
A.nnal

Technical

Conference

and

Exhibition,

Houstcm,

Cuiec,

L.:

WeUabflity

paper presented
ing Conference,
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Bichard,
icaf

12.

San

J. A.:

03

Diego,

Aug.

Companent

Energy

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Conversion

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1%9
on

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The

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from

the

Deeds,

C. T.,

and

Closmann,

P, J,:

Cdu

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Etdib,
ColWidaf

Chem-

Catalysis,

of the

Ed-

Thermal

[3.

Dubey,
tion

S. T.and

From

Minemf

SPE1nd.
14,

W=an,

M. H.:`$Asphdtine

Surfaces,

Symposium

Donaldson,

E. C.,

tetition

and

on

paper

Alter.

R. D,,

Ifs Effect

SPE

18462

21,

presented

P, B.:

Efficiency,

ac the
Feb.

19S9

23.

DIV.

Pmrzes,

(March

17,

)33,1587-94.:
J.C.,

tureby

Smafl

Dictie,

1, P.,

vestigatios

Fmkman,

19,

Igmsi&,

Energy

bution

Angle
Htier,

G.,

and

Natiof

Yen,

S.

D.: AsphaJtcne

1969)

24.

2S.

P,L.

& Ruek
T.,

(19PQ)

~usz,

T. F,:``

~=tion

Asp~tees,

and Hydrogen

oqOm&inA

en-

working

1 year

as

ex-

In

wettabllity,

elec-

andtranspoff
holds

In physical

BS degree
chemistry

Ionic

and

Elecrrophoretic
presemed

American

Properties

at the
Chernicaf

1962

of

Meeting

SW.,

Washing-

J.G.:

Anderson,

kCore

Maxhl

988)

Marchin,

of Crude-Oil

Conduc!ivilies

Fuel

W. G.:

PEFEt

M, E. and

LEIectricaJ

Solvents,

L. M.:

Asphaltene

(1974)
Cleaning
131-3

for

and

Polar

Bitumen

192-97.
Re$forationof

ETram.,

.. Weuabilhy
and

of

53,

AfME,

Adsorption

Fractions,

?J35
Char-

f,JPT(April

470-74.

Uer,

R. K.:
No.

4.

Tiffm,

sStearato

Chromic

Chloride,

Id.

& E.g.

C&m.

(1954)

766-6!7.
and Ydlig,

D.L.

SI

Miscible

Metric

Gas

W. F,:

Effects

Displacements.,,

Conversion

MicroXopichV,3.

Colloid

Cd

f12

In-

of Mobile
SPEI

Water

(1...

on

1983)

Muldple447-55.

in Afhabasca

Factors

4,184
9,29f)3M*

E03

kf

E02

=
=

mz
.~

E-01

cm

(F32)/l.8
x

2.54*

tiabmcaAphdtene,
Tonvm!m

a"d Mont80me~,

Bonding

of

Brooklvn.

Chemistry,

SWight,

ad

1560-67.

4,263-70.

359-65,

of

U.

Center

after

spent

He

in Petroleum,

Nonaqueous

in.

O. P.,

U.

former-

Research
19S8

are

degree

of

the

E& PLaboratorIum

processes.

?mlvation,

Weuabilhy,S

Contacl

Chem.

Macrostmc-

uei(l9S8)67,

P~oleum

OwgenC

from

Waxman,

Bellalre

he

degree

20-29.

and
in

(1967)29,475-84.
Z.etal.:

a BS

geochemistry,

a PhD

de-

She

in chemical

H.

In Feb.

an-

Espinat,

and

Tnv@@dcmoftheSamcDiffraction.,,
,4mz1.

NemonSc8ttering,F
M, N.,

ontie

f@Ct~Ci.

1S.

Ducouret,

Ravey,

56,

PdEack,S.S .:`
bv X-R.,

the

Interests

earth

In

Memorial

degree

1961-62,

Inst.

The

March

Crccker,

46.

T. F., Emfmm,l.G.,
and
of Pelmleum
Asr.halteIIes

(1961
16,

CWm,

1988)

.. ---

Yen,
ture

to

MS

Monroe

KoninkHjke/SheO

U. and

of Petroleum

DC,

aclerislics
De-

I ?-m
15,

an

ssnds,

Asphalrmes

Native

8-10.

Tenability

7, .WEJ

22.

Deso~-

Houston,

and Lor.nz,

on Recove~

at the 1980
Sept.
21-24.

Adsoqtionmd

OMieldChemistry,

Thomas,

p=$ented
Dallas,

and
method

ton,

~vekTars,
p.p.r
SpE9510
TAnicaJ
Conference
snd Exhibition,

degree

retired

His

Polvtechnlc

Fractions
aL:Ons~p=ce
SPE Annual

a PhD

During
the

shaly

Long

and

at

Co.,

at

properfles

from

assoolate

1952.

In

19-22.

M. H.,

since
scientist

20,

presented

Third

research

Shell

degree

and

Development

change

MS

U. of Tulsa.

reser-

Engineer-

23-29.

pap

Conference

Oct.

Waxman,

RocWCmde-OiJ

Solubfify,

Engineering

monton,

and

at the 19S6 Jntermciety

Johns,

the

from

Sept.

an

in chemistry,

from

trochemlstryof

16-19.
10,

Bombay,
St.

ly a senior

Symposium

of

all

gineering

in

by Adsorption

Enhanced

U.

Newfoundland,

149-52.

SPEIDOE

in

mechanisms

holds

227-32.
of

Propedies

for

at fhc

TuJsa,

52,

Reck

of

J, G.: Investi8afi0n

Sol.bility

studies

vilopment.

Waxman

,Amthe

with

wettablll-

alytical

from

(1973)

Alteration

presented

Oil Remvery,

1,0.:

Involved
and

voir

Components

Gcochmism.

&evier-Science

Speight,

Co.

research

Asphahic

Shell

has

EOR

701-04.

of Pwrol..n!

at

Houston,

&

1S Com-

resesrch

in

of

Clays

Heavy

SPE

1. 2fubey,

Development

ty

Wmract
ions

W!nni

CoWmbo

D.L.

106S3

1983

Denver,

Ends

24,

.Forrnatio

,,S Fuel

Fillers,
and

Heavy

SE., Fryer, J. F., and Speight,

Molecular
Weights, Fuel (1976)

Clemenu,

Wafer

197-203.

E,:

Fundnmeml

V.

Mitchell,

presented

Chemistry,

(1972)

From

(1967).

troleum

11800

Petroleum

J. E.:

Bifumen

(1980)

Moschopedis,

SPE

Clay

Wih

Hydmcarben
8.

&

and

Asphattme
7.

Clays

Petroleum.,

Nagy

6.

of

PA.

stemkn

SPE

Geothermal

Interaction

E,

Clay

4,

and

and

at the

of Asphaltenes

Adsoq8ion
paper

chemist

D ,M.:

Czarnecka,

J: C.:

Minerals,,,
on OMield

morillonite,
3.

Mekose,

Rock

D. S.:``
Asphaltene,-,

Oxygen
Fuel

Dism"(1977)

factor

O,lglnal
Oct. 23
edm

I*

SPE

nmn,cdpt

<WI

Revlse5

the

1989

SPEI.!I,

SPE32E

exact.

rece!ved

tar review

nmUSCrl.Dt recalved
Symposium

Feb. 8,1989.
SePt

on Oilfield

19, 1 SO.
Chemistv

PaPec
Paw,
held

Wcmted
(SPE

to, Pbllcaf

?3d62)

in How!on,

lo

fi,sl CU.,.1.
Feb.

510.

?$
SPE

Reservoir

!3@neering,

August

1991

395

w
ADSORPTION OF ASPHALTENESON KAOLIN
FROM NONPOLAR SOLVENTS

ADSORPTION OF ASPHALTENES ON VARIOUS CLAYS AND

MINERALS FROM TOLUENE SOLUTION

6
112 -3/2
cal cm

Solvent

Maximum Asphaltene
Adsormion Level
Per unit

weight
of mineral
mglg
9.3
8.9
8.7

Chloroform
Toluene
Toluenel
n-dodecane
(1.75:1.0 W/M)

23.8()
26.4
29.8

Asphaltene Monolayer
Mineral
Adsorbent

1
2

Illite
Kaolin
Mineral
Calcite
(Dover Chalk)
Ottawa Sand
Dofomite
(Dolocron)

W&t

25.8(2)
26.2
30.1

2.0
2.2
2.5

Thickness
nm

1.75(3)
1.9
2.2

2.4(4]
2.7
3.0

3
4
.s

Calculated from linear transform of Langmuir isotherm.

1
:=:+
a a, a,K
where a is the asphaltene adsorption in equilibrium with asph$kene concentration ca, is the
saturated asphaltene adsorption at complete monolayer coverage and K is the ratio of rate
constants of the adsorfxionldesorption reactions.

(3)Calculated from ncorrcc~ed Bnsrface

area of 11.9 m21&density ofasPhahenes

equalt0

~~~/21

Monolayer
area ~
mglm

) From isotherm plateau level.

(2)

No.

Dickite

Berea Sandstone

Alumina
(Type A)

())MoolaYer

WtAVt() I Wt/Surface.Area

mvg

mglg

37.0
11.9

39.?

mglmz

26.2

1.1
2.2

1.71

5.8

3.4

1.69
2.87

3.70
3.75

2.2
1.3

0.88
1.48

1.84

2.1

1.s2

1s.9

1.0

19.2

1,2

~eight~~b(ained
from linear transform

of Langmuir

Type I adsorption isotherm,

(2)

BET surface areas using

ei!her

nitrogen

or

kryptcm.

1.14.5 g/cc.
(4)A=me~ o edge ad~O~tiOn wjth p]aar 3UrfaCe area eqUal tO 0.9 Of tOtd surface area; also.
asphaltene packing fraction e~ual to 0.8.

32blcQ
ADSORPTION OF ASPHALTENES ON KAOLIN
FROM NITROBENZENE

No.

1
2
3
4
5
6

Equilibrium
Asphaltene
Concentration

ADSORPTION OF ASPHALTENES ON VARIOUS CLAYS AND

MINERALS FROM TOLUENE SOLUTION
(Based on Adsorption from Asphallenell%lee Solution, 2500 ppm)

Asphaltene
Adsorption Level

ppm

Mineral
Weight Basis
mglg

Mineral Surface
Area Ba;is
mgJm

1411
1087
750
511
362
151

91.3
71.7
64.4
56.g
49.9
33.4

7.7
6.0
5.4
4.8
4.2
2.8

Thickness of
Absorbed Layer
nm
Alumina (Type B)
Calcite
(Omya)
K&liriiti
(TWiggs)
Thuringite()
Chlorite(l)

6.7
5.3
4.7
4.2
3.7
2.5

m21g

mglg

mglmz

114
12.3

174.7
21.3

1.1
2.2

10.s

20.8

3.4

9.1
3.0

2.2
1.3

8.13
0.73
1

(t) Leached ~ith buffered sodium dithionite 10 HItOW

and water washed.
(2)BET surface ~reaS usin8 either nitrogen 01 krypton.

irOIt

OMea

~PE 18462
IRREVERSIBLE Adsorption
OF ASPHALTENES
ON KAOLIN FROM TOLUENE

SOLVEXT CLEANING OF SILICEOUS CORE MATERfAL P-FID SCREENING METHoD

Irreversible
Equilibrium
Adsorption
Level on Kaolin
mg/g ( ] )

Adsorption
Level After
Proton ed Toluene
\$ashin
mglg ( f )

46

17.1

375
593
1381
2160

25.9
26.8
26.3
26.1

19.0
19.3
21.8
23.1
23.0

Equilibrium
Cone. cd Asphaltenes
in Toluene Solution
ppm

(1)
By

Percent
Asphaltene
Retained
Afler Washing

74.5
81.3
87.8
88.1

Absorbance method

2) By P-FID

\Veight Percent Pyrolyzable

Hydrocarbons by P-FfD
< 100C
400-750C
Total

Solvent

method

\Veigh! Percent Hydroca

Removed by Extracti

None

0.525

0.099

0.624

---

Pyridine

0.038

0.008

0.046

92.6

Tetrachloroelhyl~ne

0.050

0.023

0.073

88.3

(1) Tofuene
(2) C!!ClJCH30H

azeotrope

0.013
0.002

0.022
0.002

0.035
0.004

94.4
99.4

(1) ,Methylene Chloride

(L) CHCIJCH30H azeotrope

0.08
0.001

.0.02
0.001

0.10
0.002

84.0
99.7

(1) CHC13
(2) CHCIJCH,OH

0.002
0.004

0.006
0.003

0.008
0.007

98,7
98,9

0.004

0.003

0.007

98.9

CHCIJCH30H

azecmope

azeotrope

Table 10
tiSBM WEITABILITY TESTS - BEREA AND BENTHEIM SANDSTONES
USBM Index W

Treatme-!

TfRREVERSIBLE
AFTER

ADSORPTION
REPEATED

SOLVENTS

No.

Solvent

OF ASPHALTENES

\VASHINGS

OR SOXHLET

8
1,2 -312
cat cm

WITH

+0.97
+0.99

+0.90

Adsorbed Asphaltenes

+0.12

+0.43
+0.51

VARIOUS

EXTRACTIONS

[ni:ial
Adsorption
melt

Final
Adsorption
mele
31.4

Percent
Asphaltenes
Retained

Freon 11

7.6

30.7

Tolueneln-Dodecane
[1.75:1.0, Wlhm)

8.7

30.K

Taluene

8.9

30.8
29.2

25.5
24.6

82.8
84.2

Chloroform

92

30.6
30.7

18.3
17.9
16.2

59.8
S8.3
S2.9

Chloroform/Acetone
(70/30 Vol)

9.4

30.0

8.2

27,3

Methylene Chloride

9.8

30.8
29.9

21.4
22. I
21.2

69.5
73.9
70.9

Chloroforml!vtethanol
(87/1 3 VOl)

10.5

30.6

16.2

52.9

Pyridme

10.6

30.6
30.3

6.7
4.1
2.4

21.9
13.5
7.9

-1oo

Chhwofmmlkfethanol
Azeotmpe
(78.7 /21.3 vol)

10.9

32.8
32.8

1.6
1.0

10

Nitrobenzene

11.1

3J.K
29.8

-18
21.5

58.4
72.1

11

Chloroform/Methanol
(70/30 Vol)

11.5

30.8
30.0

6.9
11.2

22.4
37.3

12

ToluenelMethanol
Azeo!ro e
(29. U7{.9 VO])

13.7

31.7

22.8

71.9

a)

Bentheim Sands

Heated, 550C

OS KAOLIN

b)

Berea Sands

00

4.9a
3.ob

By repeated washings
Soxhlet exactions
Note:

Initial adsorption on all kaofin samples except NoF.. 4 and 7 from 3000 .Dpm
.
asphaltene solution in tolueneln-dodecane (1.75:1.0 wtlw).

r
o

Initial adsorption on kaolin for samples NOS.4 and 7 from 27,000 ppm asphaltene
solution in lolueneln-dodeca~e (1.75: LO wlwt).

10

20

30

TITRANT (n-OODECANE)
fig. l-Blcfurd

40

TO ASPHALTENE

titmtion test for nphdtwrw

50

60

RATIO, mllg -

In rronpolw Mtwnt9.

SPE

~
~

3028-

24-

20-

16-

EI TOLUENE/n-DODECANE

12-

(1.75:1.0

W/W)

0 TOLUENE
a-

A CHLOFtOiXOWf
Q NITROBENZENE

-f

400

800

1200

1600

2000

EQUILIBRIUM CONCENTRATION OF ASPHALTENES,

Ftg. 2-Admrptlon

2400

28

ppm -

Ieotherms for sphrdteneeon keolhr from different solvents.

EITOLUENEln-DODECANE

(1.75:1.0

(wIw)I

@TOLUENE
A CHLOROFORM

400

800

1200

1600

c (mg/1000g)

2000

2400

2s00

Fig. 3Llneer trarreformof the Lengmulredeorptlon Ieotherme for eephetteneeon keolhrfrom nonpolar8olvent8.

60

184(jz

m
*

jQ---.

0
0 BEREA SANDSTONE

(>100

MESH)

A DICKITE (WISCONSIN)
DOLOMITE (DOLOCRON)
OTTAWA SAND (SUPER x

>325

MESH)

C) CALCITE (DOVER CHALK)

KAOLIN MINERAL
M ILLITE (BEAVERS BEND)
0 ALUMINA

~
1000

2000

EQUILIBRIUM ASPHALTENE CONCENTRATION,

Fig. 4-AdwQtlon

ppm +

of asphaltenes on clay and mineral wrfacee fmm toluene.

El

500

1000

1500

ASPHALTENE EQUILIBRIUM

2000

2500

CONCENTRATION, ppm +

Fig. 5-Adsorption.desorption hyetaraala for aaphaltenaa on kaolin from toluene.

61

10

5
65
Il.
Ill
u

ii
02
go
0.

B...

. .

..n

$
BRINE

a
-J
d
E

DRIVE Ab /

BRINE

DRIVE Ab /

-5

0.2

0.4

AVERAGE

0.6

WATER

UNTREATED

0.8

-lo

0.2

SATURATION

I
0.4

AVERAGE

BENTHEIM

ASPHALTENE

Fig. 6USBM

teets, Bentheim

62

sandstones.

0.6

WATER

I
o.8

SATURATION

TREATED

BENTHElM