Permeability

by

Modification

In-Situ

Newly
Shapour

Gelation

With

Discovered
SPE,

Voasoughi,

and

Biopolymer

C.S.

Buller,

of

Kansas

t~b3\

%PE

Summary.

In a typical

of the process

depends

agent.

Controlling

is therefore

gelled

those

desirable.
KU.

pentoses,

disaccharides,

The

gdation

produce
or such

remains

associated

with

is cxtractid

from

the bacteria

as a hydrogel.

formed
and

the

flushed

with

then

State

of

Early

polymer

tion

of

The

to reveal

the

subsequent

procedures

solutions

and

reservoirs

by mecbanicti

and the tendency

chanical

entrapment
Thus,

retained

is insufficient
period.
recent

shear,

from

high

in wxous

of polymek.

media

the components,

times

temperature,

PH,

metal

other

be controlled

to some

extsnt.

resultsin

nique

may

prcduce

satisfactory

fails

in most

field

applications.

Additionally,

permeabtity

of the

the

in sites
farther

near

the

removed

a result

of a large

namber

here.

The

ride

produced

by Cellulomonmfivigena

thin-layer

chromatography

determination

of glycosidic

bonds

it is not hydrolyzed

that

use

of the

and

the

polymer

amykases

strata

tie

was

was

water

formation

The

precipi-

coreflood

initially

in in-situ

medium.

the polymer

A linear
core

of hexoses,
The polymer

growth

extracts,

polymer

of hat

im subtemammn

concen-

of the

Strain

per-

flooded

of hydrogek.

biopolymer

that

for use in inGas,

acid

liquid,

was not determined.

type

Because
U. of Kanof polymer

another

and

was

tier

cellulose.

It has

flzvigena.

12
were

Collection

(ATCC)

in

CeUdomongsf7avigena
medium

extracted

a 72-hour

were

resulting

neutralized,

containing

and
the

cell

culture
the

in

cultures,

poly-

in 1 N NaOH.
alkaliie

in precipitation

of

as described

of the

debris,

was

an excess

purified

incubation

by resuspending

Af-

supematants

of the

polymer

in gel

fem.
cultivation

(ATCC

of Afkafigenes

#28180)

iq a minimal

of the polyglucm

Ha.rada
The

polymer

used

crude

The extracts

After

subspecies

faecalis

medium

produced

containing
was

Txogems

glucose

performed

and purifi-

as described

by

et al. 13,14
in the

extract

were

with
brief

made

described
cycles

batch

in Table

cultures

pcdymer,

the

was used

typically

alkaline

cell

weigbi)

residue

supematant,

for the coreflood

contained

the sedimem.

(wet

the

was
washes.

of C. jfavige-

1, and extracting

temperature,

and

below

of water

by use of 8 ML alkah/g

at room

by centrifugation
extm@

test

by many

by centiging

1 NNaOH
Siring

coreflood

purified

as described

on the

mo~lcation.

Viscometrfc
Model

Measurements.

R19,

equipped

the viscosities

eels.
W$

,re-

conmmmg

experiments.

Such

1.5 to 2 mg polysaccbarideAnL.

mine

of operating
mode.

11

The

the elastic

polymer

solutions

were

To maintain

circtiator
berg

performed
performed

bath

and

platen

rheogoniometer
attached

to the

this

was

mode

under

Data

achieved
control

to measure
is capa-

or a sinusoidal

was

nsed

modulus,

to deter-

which

char-

All measurements

temperature,

used.

ISAAC

mode

steady

at a constant

a set of flexible
were

gel.

used

The instrument

the storage

of tie

rheogoniometer

was

rotational
testing

and

behavior

plate,

and gels.

oscillatory

were

Weissenberg

and

a steady

viscosity

acterized

to the lower

cone

solutions

in either

the dynamic

(+0.4F).

The

with

of polymer

cal measurements

we concluded

1! and

permeabtity

Culture

(CM9)

poiymti

etiacted

oscillatory

of the poly9 The

or cslhdases,

Type

Furiflcation.

to remove

ble

hydrolyzates

mntsnt

to hydrolyze
of Celhdomonas
and Alkdigenes&ecdis

time
proc-

homopolymer.

process

was

the dissolved

the gelation

KU.

polymers

and

9: fn brief,

moved

is an exopolysacch?.-

sugar

aad

ed cells

am

requires

the

has potential

American

Synthesis

alkaline

discovered

the

nu, PrePa@

greater

which

including

of its ability

ter centigation

XT
.Materlaka

from

The

variables

MD.

cell-free

be

failures

a starch nor cellulose.

The
patents:
one on the process

product

can

require

is independent

reducing

in the polyglucaa

that the polymer

is neither
sas has been gmn~ed
two
production

Ref.

it

success

agent.

it is a glucose

by either

tests,

The

and in which

of tie

of the total

indicate

process,

and therefore

is described

saccliaride

for gsowth.

as a new strain
of Celkhwnas

in a minimal-salts

cation

is experienced

which

on the basis

from

The

of

the tech-

some

success

of the

A newly

in-

and phys-

@though

strata.

step

and
and

litter

PoIymef

a 3D cmss-

chemical

porons

are added

is desirable.

to yield

subtermrmau
little

reducing

the geMion

requirements,

situ gelation,

fewer

one of a variety

temperatures.
resulted

with

by CeZhLmwnmjLmige-

sny
out

success

and reducing

sources

of such

process.

been charactefied
AU other spycks

grown

the

typ&lly

while

of variables,

and

components

ess is reversible

the

complexity

polymer,

in which

these

for

laborato~-scale

the wellbore,

into

of the

of ions,

wellbore,

tlom

penetration

individual

at high

of the polymer

glucose,

by concentrations

and/or

and cm

meets

a peiicd

large perand rn-

crosdinkiu

ions

ical factors

A process

solution

to settle

neutralization
gelation

Rockviie,

polymer

to producs
process

with

thst

and

energy

The

polymer,

a prncess

produced

containing
snd

system.

ions,

water

reduction

involved

are influenced

control

in-situ

obtsiicd

or me-

of iatxt

A polymer-gelation

of the polymer

trations

or resident
by adsorption

in attempts

Gelation

gelling-agent

Upon
are stable

the

mer
used

reaction

the

degrada-

permeabilim

system.

mostly

to some
ilcmdmg.

the amount

to maintain

or

polymer

injected

volves

in sites

works

the FOrmIS rock over

reservoirs,

processos$g

in modifying

medium

to aggregate

leaf

the i@flooding

are polymer

retained

tiom

simply

technique

Iiied

achieved

for

of an alkaline

polymer

failures

of polymer

in hay

reductions

situ gclakon

The

to be washed

of time.

More
rneabilitv

called

for these

salinity,

desired

polymer

injection

do not benefit

responsible

caused

and the hydrogels

1-3 involved

was

watertlooding.

but maay
factors

tion

acid.

is reversible,
microbial

salts

biopolymer

as the carbon

alkali.

the

cross!.inkd

Devising

impossible.

discovered

in a simple
them

a 3D

if not

or molasses

in dilute

to yield

of the metal

a newly

causing

ion

the concentrations

Arf

polymer-augmented
Some

process

cultured

by suspension

a metal

difficult,
uses

as starch

bacteria,

easily

of using

The

when

producer

feasibility

treatment

polyiner

extent,

the

gelation

is eytnmely

sabstmtss

with

inch!dmg

in this paper

the biopolymer

polymer

reacts

of variables,

tests

process

inexpensive

prcduced
tates

a polymer

number

in field-scale

in-situ

bacteria

process,

a large

variables

The

na Strain

polymer

on monitoring

silicon

shear.

on the
Theologi-

tempemmre

of 77F

a constant-temperature
rubber

heaters

acquisition

from

the

by an fBM

personal

attached
Weissencompnter

system.

Methods
Results

Bacteria.
used

The bacterium

in most

that produces

of the experiments

the polysacchwide

described

here

was

polymer

isolated

born

Polymer
KU was

Cowrlght 199t Sc41@lyof

Pe!m[eum

E;gleers

descnied.

Chemicsl
grown

and

Physical

and polysacchtide

9 When

alkaline

exmacts

fioperties.
extracted
of tie

C. j?migena
from
cells

Strain

it as previously
containing

1.5%
4a5

TABLE

lSAMPLES

OF

POLYMER

VISCOSITY

NaOH
Sample

. ..*

._

0.1

0.1
+: :

FOR

103
,Omd.fe
. smu!.1,

NaCl

Polymer
(%)

s,mow

0.0

0.0

smote!
so.,,,!

10,000

102

0.1.

~:

O.T

0.1

50,000

**

7,

0.1

100,000

1.0

%
&
>,

1.0

10

1.0

11

0.0
;

0.0
10,000

1.0

20,000

12

1,0

30,000

13

1,0

50,000

14

,1.0

100,000

m
1,

x s~~*,~t,~

z:g

... -

1,

(ppm)

0.1

SOLUTIONS

MEASUREMENTS

10,

gB

E,

Mm:

.
8.
o

wt/vol

or more

dialysis,.

their

washed

water

for

gel could
result

thereafter

still

regulation

The
cose

with

sulfoxide
spectra
ing

13C
each

polymer,

within

row,

consistent

in ffieir

certain

inand

in NaOH

,f&?cdis

of the polymer
were

cycles/see.

virtually

identicaf.

and
with
coil

the
the
form

other.

No.

etiacted

of samples
21680),

from

1.0

RfIealogfcaf

lle

spectrometer,

NIvfR

spectra-of
lines

lines

of the

Ml the spectral
that

the

dissolved

weze
lines

uolvmers

NMS

two

pared

at 60,000

and

80,000

observed

that

polymer

left

and

spectra

were

nar-

woufd

at room

be

in D~SO.

ments,

with

Polymer

in

present

ppm

NaCl

increasing
concentration

to check

of

in the sohdon.
At the

to be more

stable

ent changes

in

some

The
than

color

those
with

1 week

samples

samples

the effect

ppm.

to be more
on blahk

More

bad turned

prep&d

and

ppm
was

Polymer
tolerait

to

samples-i.
solutions

meas-

measure-

brownish
showed

e.,
were

viscosity

viscosity

in 1.0 N NaOH

in 0.1 N.NaOEf

of sak

No polymer

100,000

of the

soPI*

at 60,W?il

The polymer

time

varied

fmm.tbe

started

seemed

for about

that

were

in
pre-

were

salt content.

performed.

precipitation.

2 were

mecivitated

precipitation

temperao.ma

were

solutions

in Table

llvo-addit~onalsamples

at 1.0 N NaOH

we noticed

slight

solutions

of polymer

given

above
50,002
ppm NaC1.
measurements
were ASO made

@ymer

urements

NaC1.

at a salt

prepared

saft contents
Viscosity

stored

p~rn

increased

in solution

the

polymer

Salt concentrations

NaC1.

at

NaCl

IO0,C410

vvm

lution
It was

of

Samples
saft contents

measurements.

0.0 to 100,003

without

obsewed

the different

for viscosity

from

observtwo

Characterization.

with

pared

behavior

NaOH.

solutions

dimethyl-

of 100 rnghnL.

Six spectral

were

C. j7avigena

in deuterated

XL-300

expectation
~hen

spe-

or no b~anch-

(ATCC

corresponding

of each

little

spwtm

The

a glu-

by Alkdigems

(NMR).

dissolved

on a Varian

and its abili-

Agrobacterium

with

at a concentration

0.5 ppm

random

A.

polymers

at 75.4x106

were

and

resonance

from

recorded

were

remain

of curdl~,

excreted

,3-polyglucan

magnetic

(DMSO),
were

polymers
for

myxogenes

those

Both

KU.

Fig. 1 Vk?cosNy/shear-r8te

doss

24 how-s

of dissolution

and

10:

,-

at

hydrogels
they

to those

rate,

UL

sedimental

of the polymer

similar

prcduced

produced

compared
Strain

cycles

insolubility
traits

is a&l

nuclear

of curdkm,

such

I
10

Shear

NaOH

ire

13.14 Curdkm

ing. 15 ?he

Headng

100

were

cemifuged

of the

at 261 F for at least

repeated

water

hydrogels
subspecies

cies.

then

gels

I
10

10

or by

acid.

homopolysaccbaride

faecalis

weight

or C02,

these

of the polysacchaxid~

withstand

chmacteristic

ty to form

and

of *e

for as water.

acid

When

impurities

98%

in an autoclave
by

with

congealed.

to remove

15 minutes,

in solubilization
heating

neutralized

volume

be accounted

tact after
and

were

entire

with

15,000xg
not

polymer

red with
seemed
no aoDar..

time.

70

70

,oo~
100

10
shear

F[g
I

i3:INI;0H.

486

Vwoaltylshear.rate

rate,

behavior

100

10-

10

~!

104

,-
of polymer

Shear
solutions

,llllll.(!!llll
103

10

10

rate,

s-

in
~9.

S=6hear-senshive

behwior,ot

WE

Reservoir

polymer

solution

E@ne~;Nc.vekbei

Sample

6.

1S+1

10+
$1

show m,,

1:

0,59 $-

:
.~
&
#,
2

,Sj 10

.9..
9

*.
.9 .

*.

70
o

24

!.,

10

to

Time,

lg.

4-Steady-shear

viscosity

Shea,
of the

gel

Fig.

The b~samples
were

1 cp.

Newtonian,

2%

polymer

bad

no effect

with

viswsities

on solution

be fiatior

re~onding

with

a vis-

in LO N NaOH

also

around

2.7

and

5.7

(Fig.

1).

The

presence

cp for

1 and
of salt

viscosi~.

with

in 0.1 N NaOH

a viscasi~

of2.7

at 0.1 N NaOH~

m.

the same

soluti&~&
however.

afso

exhibited
as the cor-

&t

behaved

of the

differentiv.

POIYThose

wcs

shear
sbezr

fia~l.

The
of n=

The stable solutions

exhibited
Newto@im
bebavior,
with approximately the same level of viscosity
as that observed
for 1.0 N NaOH

levels.
Dynamic

polymer

formed

semitive,
low
rates
initial

as Fig.

shear

rate

aftered

3 shows.

of

7.5

to the sample

polymer

We

seconds

up to 750
rate

of 7.5

and

seconds

shear

four

times.

Fig.

ning
high

~d has a lower viscosity

shear rate of 750 seconds

3 shows

produced
.1

low

solutions

the

3 by

applying
-1

seconds-1.

that

Fig.

were

wmple

after each
1.

and
The

starting

increasing

then

returning

cvcle

becom~s
time

also

was
less

shear
at a

it is exposed

Fig.

fmm

viscosibj

6 presenk

ppm

NaCf.

tem,

also indkated

2%

modolus,

polymer

Constant

with

G, vs.

G is an indication
by the zero

Gels

dynamic

a power~law
vkcosim

produced

the same
samples

of
&tb

viscosity
were

per-

of the gel systems.

frequency

for tie

in the presence
of z perfect
viscosity

rate
20.000

with

audlor

behavior

in 0.1 NNaOH

in 1 N NaOH,

strenztb

of the gel

while

4, which

stress/shear

bef&ior,

exhibited

the vismelastic

storage

to the

from

normalities

time

Ffg.

NNaOH

of p~.

measurements

to characterize

shear

under

sensitive,

with

polymer

ii 0.1

to be a function

gel.

of tbe gels

vafue.

2%

The

the

to be shear

5 plots

sh&&&dmg

of different

duced

from
Ms.

is revealed.

not Smrn

solutions

found

decreased

2 % ooltier

strong
O.47.

shear
remated

sh&

icid

were

an equilibrium

this behavior.

of

the viscosities

The gels

for a gel produced

for a >el umduced

eimnent

to measure

it reached

ilfustmtes

ppm

behavior

of the gel continuously

until

generated

clearly

t@ gel does

The

made

conditions.

and the viscosity

under

smnplos
fiti
color change
and partial precipitation
prcd&d
much
larger
viscosities
with apparent
shfxu-thinning
behavior
(Fig. 2).

solutions.

, .-

5Shear-stres9shear.rate

Attempfs
steady

was

(1 % v.I/vol)

1.0 N NaOH/polymer

solutions

behavior,

of polymer

respectively

of polymer

Newtonian

Newtonian

Solutions

content,

Solution

me;

all exhibited

of around

rate

vs.

ime.

cosify

10

100

minutes

measurements

,11

~ ~

10-

gel proof 20,000

elastic

reported

sys-

in Ffg.

7.

thinto the

Lfm?ar
Berea

Coreflood.
sandstone

The
core.

coreilocd

The

tests

core.,

from

were

performed

a rectangukw

cross

on a l-ft
section,

10

10-

10
Hz

Frequency,

Fig.

6Storage

SPE Rcsermir.Ea.@er@,

modulus

measurements

November

1991

10

Frequency,

of

the

gel.

Fig.

7Dynamic

viscosity

Hz

measurements

of

the

gel.

487

was

enclosed

by.a

layer

of the experimental
core.

llrs

ppm).

core

initialfy

The brine

ration.
The
Wasbingmn

was then

8 and

represented

the

CIU31S.

&ta

lines,

of 27.5

core

was

8 shows

a sharp

mer

injection,
amount

in ffow
reversibility

N NaOff

into

injection

tion
did

rate

was
not

were

fn @ose
from

after

experiment.

not

of in-situ
resulted

and

is

acid

as an indication

in+itu

gels

for the
lines
experi-

At that time,

breakthrough
solution
drop

gelation.

The

of a 50%

increase

decreased

of poly-

injection

of am ad-

drop

in pressure
cm3/s.

slug
drop

containing

of the NaOH

was

the ge!k.d

solution

resulted

at the beginning

of sdkafi
to soak

was

stoppsd

into
the

tested

was

a 10-fold

the
gel

by injection

polymer.

Fig.

core
in the

in-place

for 2 hours.
core.

of 1

8 shows

in reestablishment

of the experiment.
and the

This

that

core

injection.

was

stilf
This

during

The

drop

the fmt

and
was
w

36 psi.
break-

that

the flow

rate

dro.s

patialfy
implies

therefore,

plugged
that

the attempt

core,

then
then

water

in the pressure

treatment.

developed

to its initial

after

difference

the

NaOH

to dissolve
W2S nOt con-

coniiition.

declined

and to about O cm31s after

was 38 psi after the segmd

to 0.0027

injwtion,
Fig.

cm3 /s after

the second,
slug. These

and
rwts

the fkt

that the pressure

implY that dug

of polymer
and whole-core
polymer
flocding
injwtion
be of eqti
effectiveness
in permeability
redyction.

We

feel

newly

NaOfi
This

of
At that
solusoaking

and

that

two

and

titmtion)

methcds

IWY

subterranean

@o

oil

that might

advantage
Perhaps
efficiency

ratios.

(increa.wd

formation

advantage

solubifity

flocding.

of the alkaline

mobility

properties

associated

solutinn

of the

witi

vismsilv

alkaline

of in enhancing

this

in dilute

solution

by acid

oil production

from

reservoirs.

polymers

cosity

gel

be taken

Remarks

physical

polymer

revers]%le
an

to alkaline

Concluding

inherent

ducovered

The
gelation

2 of the mme-

Two slugs of polymer

injection,
each followed
by acid
were tested for effectiveness
in perrneabfity
modification.

state

fbus,

rate.
of in-situ

by NaOH

restored

Dhcusslon

at the time
increase.

in pressure

27 psi.

have

D.v

the pressure

observed

of the first-day
may

occurred.

in 1.0 N NaOH.

to 0.C029

1) was

drop

is taken

plctely

of treatments

fmt saturated
with the brine,
water samration.
Waterfloo3

breakthrough

(Day

discon-

of the

at water

through

for which

broken

the sermence
core was
to connate

the pressure

channels

avaifable

recurred.

in a fiuther

rate

dissolve

initiated,
fn contrast,

flow

indicate

instances,

9 shows

flood test. The

01 was injected

as a cxm.wquence

fluids

for events

the outset

in pressme

and the flow

observed

allowed
tier

lines

breakthrough

increase

the core

the flow

of the

me made
data

of events

of pa.gicular

broken

as a 2 % wUVol

of acid

The

and

was bqm

indicative

the consequence

time,

sam-

psi was achieved

with a flow rate of 0.0306
acidized
by the irjection
of acetic acid,

Fig.

that

(10,MIO
water

the

then

was injected

to 44 psi,

b$stmies

began

water

fbmding

the flow

iolution

the sqmmx

injection

flow-rate

until

polymer

decrease

Fi=.

and

indicates

and polymer

drop,

components

gaugez,

mints.

The

dkionzl

a brine

9 present

flow-rate

of the core

drop
me

8 and

end of the ev.mt.

and condnued

a pressure

principaf

pressure

by oif to its connate

Exceptions

and/or

andlor

Waterflooding
ment

displaced

aqd

by unbroken

the pressure-drop
connect

The

with

9, the continuous

in the injections.

beginning

saturated

Figs.

the pressure-drop

tinuities

a pump,

was

at 660F.

In Figs.

resin.

were

01 used
was fmm
the BartlesviIle.Dewey
tiefd
in
County,
OK, and had a viscosity
of 8 cp and a gravity

of 35.4API
and

of epoxy

setup

makes

the polymer

solution,

it provides

enhance
Tbe

in alkali

Because
sweep

of being

both

the most

importznt

is the variation

factor

of rock

and
that

Rewm.ti

witi

proposed

a polymer
zffect.s

penneabiity

additive

increase
favorable

in cases
floD6

an alkaline

SPE

a more

eftitiency

alkaline/polymer

it attractive
would

unfavorable
here

has the

flood.

volumetic

with

E@Jeerims,

the vismobfity

spatiaf

sweep
position

November

1991

in the reservoir.
fecdve

The

technique

blocktbe

presented

to medi@

already-swept

placing

fluid

zones.

(water

for the pelyrrrer

tinued

until

selution

to fr~h

wafer

welfbere

zone

free

acid

ti

solution

solution,

Obviously,

the

mer

is not

ae a capsule

a variety

prepared

of

to eliminate
bacterin

in in-situ

may

subsequent

indigenous

of highest

such

17 Bacteria

tfrerr iqjected

result
indigenous
into

of the bacteria,

pernreability

they

zones

Plugging

wefls.

only

irr the growth-aswoiated

unwanted
in the

microscopy

the

process.

reduced

For

size

that

ity of oil-bearing
the

reason

do not muse
rock

from

alkaline

extracts

has

been

solubilized

may

PhD

1620

we

in which

non-

reductien.

U.

Oraok

David

of Kansas,

Van&r
for

Velde,

determination

starved,

and

reduced

nnd through

the

the bighreduction.

introduced,

resulting

of rhe

cells.

Buller
of

Kansas.

He

the

U.

of

Kansas.

His

that

celk

et al.:

GMeld

Butter,

C.S.

tacclhdar

Al-

tech-

U.

of

Ksn8s8

t 986-89

and.3
Pregram

Is a professor

[n the

holds

BA,

research

lipids,

Dept.

MA,

and

Intefssts

and

blorsmed-

of

removing
poly-

laboratory,

spectra

13.

and

VoeP4,

paper

SPE

16253

Chemistry

K.C.:

by

p~ented

Conference,

Tro6ucdon

FmdmeA

and

Gels
at the

San

2-3,

1987

Antonio,

Fnri6cation

Feb.

of an

Celfukmwna.sf7.m@ na,

1990) 5, Nos.

1990)5,

Hti,

T.

saccbaride

et .1.:
ty

Ex-

> J.

Id

139-46.

Nes.

2-3,

Tmd.cdon

125-30.
of a Firm.

Resilient

ofAfkalizmes@ecaOs

a Mua@4

GA-forming

Poly-

var. myxogem.

10C3,,,

Agri~ti
h Biobgicd
CSrem (1966) 30, No. 2, 196-98.
14. Hera&, T. staL: GmwthaudI%Glucan
10C3KFmducdcm@a
Muram
ofAIkcdigenes fwcalis
var. my%ogenes
in Defmd
MeAium,
Agriculnual
15.

& Bidqical

Hmada,

T.,

CRem.

MisaK,

(1966)

A.,

30,

and .%.@

No.

H.:

8,

764-69.

Curdtam

A Bacterial

Gd-

forming 1%1,3-Gluwn:
Arch.
Biochmt
~OP&.
(1%8) 32A, 292-98.
16. Knapp, R.M. er d.: .Pm-Test
Smdks and Design for a Microbially
JManccd
Oil Recovery
Fietd
pilot,
paprpresmted
at the 1989 Tertiary Oil Recovery
Conference,
WM&
KS, March 9.
17, Cusack, F. et 1A.: Formation
of UIrmnicrobacteria
to Enhance
Oil
by Selective

pxium

Solutions
B.B.
and Gmbam,
G.A.:
fnjecdon
of Polymer
in 3rmiucins Wells,: $AJ~Symposiwn
Sen.es 127(1972)
6P, 38-40,
Feb. 20-23.
2. Wbbe, J.L.,
Geddard,
J.E.,
and Phillips,
H. M.: Use of Polymem
To Control Warer production
in Oil Wells,s, JPTeeb.
1973)
143-50.
of Polymere To In3. Dabbous,
M.K.
and Elkine,
L. E.: Pre-Irjecdon
crease Resmvoir
Flooding Efficiency,
paper SPE 5S36 presented at
rhe 1976 SPE Symposium
on Improved
Oi Recovay,
TkIsa,
March

Geatbennal

(April-bfay

fkcwery

1. Sandiford,

and

PolysIuwn

Microbiol.

of Polyac@mid&Cr+6

Cbaracrmization

WOR,

10. Bulk,
C.S.: Water Insoluble Polysaccbaride
Polymer and Methods
Tbermf,
U.S. Patent No. 4,90S,310
fkfarcb 13, 1990).
Permeab~
Mcditi11. Vmwwbi,
S. and Bulter, C. S.: Subrmranwn:
carion b; Usim Micmbid Polwaccharide
Pohmere,
U.S. Patent No.
4,941,533
(Juii 17, 1590).

12. Angelo, R., Vce@,

K., and EmUer, C. S.: Tsotatio.
and Characterinuion of a New Strain ef CelIukmonasJZavigem,
J. Ind. Microbiol.

References

S.

exopcdysaccharides,

fer Reducing

(APri&May

in the Wrmeabil-

of the NMR
NbfR

9.

the extraction

be necessary.

director

EOR

Technlcsl

U.

of

charasterlzs-

was

Meeting

U.

all in chemlare

during

the

from

S.K.

Used

The

by a recent

Acknowledgment

We

sf

mlcroblal

S. Nanda,

pelY-

that

the

MS

degrses

Iatlon.

of extracelhkr

believe

Annual

Clarsrrce

Include

of

upm

the polysncchnride

from

rheologlcal

sponsor

from
and

U.
PhD

Vossoughi

faculty

1986-S9

degrees

4-5.

of rekmrte

Mlcroblology

SPE

decrease

degrse

Interests

and

fluids.

Chapter

et

twawch

holds

plug-

size of the bacterial

because

not

of

in a prominent
reduction
in the
structural
integrity
tbmugbout

an unwanted

forroation,

cells

mer

and

Committee.

The

the

that

primaIy
slmulatlon,

non-Nwkonlan

then

tbe con-

to demonskate

of the enrapsrdated
bacteria
resutts
size of the ceUs and that they retain

Student

and

is initiated

were

of

SPE

and wLJ flow

permeability

nutrients

incrense

electron

into

Nen

celfs.

applications,

isolated,

His

numerical

member

unwanted

starvation

flowed

any

when

were

engbrserbrg.

niques,

was

on the use

sopport.d

Bpuse

readily

witbeut

marred

We used

m wells

the

eal

or

rdier

BS

berta,

tdo-

starch

alkzfi

uller

Vowrughi

the
In

He

and

tim

in rmconmnlkd

pmmeability

is further

at
Kansss

Tehran

attached

similar

metabolizes,

of

of
poly-

the

with

Growth

in in-situ

with

In
Chem.

Petroleum

l.awrsnes.

corn

to the we13 nre injected

appficztions

back

that

of

U.

bacterial

celf size and the export

activities
of these

as

In surh

of the required

and

can be cultured

reportbf

suggests

permeability.

led

assa-

prefsssor

cnntzct

for

be involved

problem.

Dept.

by centrifugation

A recent

EOR

the

pelyrner

with

debris

it rnigbt

be a great

of increased

f~bifity

size

that

formations.

innuduuion

sequence

the cdl

rnicrobid

bacteria

irrtn @e zones

paper.

rock

not always

growing

mers.

bacteria
the residual

clste

Engineering

d~cribed

to remove

the possibiily
of the

than

such

is mn-

Ore near-

remains

the bacteria

in the cereflocd

for removing

plugging

simpler

A@

IS an

k then

avaibbility

of the

vOs-

sorrghi

of pelyrner-

Because

but

eneapsufated

the mixture
reason

in the

medbm

ShaPour

mne.

sc.de.

subsuates,

wed

and

upon

lies

larger

much

water

Injection

separation

gum.

inexpensive

by estmwting

principaf

process

to

required

Injection

already-swept

growth

becomes

seltion

cen~giog

ging

the

the

in gelatien

the

of the

as xanthan

molzsses.
fbe plm~r

restdt

the bacteria,

medium
such

flowlines

en a nrncb

into

around

its cultured
in

success

of Ore acidic

solution.

ef-

and

the pH

that

blcwking

polymer

secreted

polymers

then

than
well.

acidic

and

the pH of the dis-

production

to ~ure

wi!l

a simple

heterogeneity

is lower

fnjection

in the
tlom

thereby

an ioexpemsive

cases)

to gel.

switched

provides

3n this approach,

in most

it is detected

ic alkaline

precess

Ore permeability

in 08s,

1S. MacLed,

Plu@ng,

OiL

F.A.,

and

Coal

hp@l&Ott,

of a Mcdel

Reck

System

Micmbiol.

(Juty

1988)

by

Plugging

1989)

4,

and

No.

at the

198S

Using

Staved

Bacteria,

IGT

Sym-

D=. 5-7.
pbl@llS

Appl.

Ennron.

54, No. 3, 1365-72.

19. Raiders, R.A. et 01.: Selmdvity

Berea Sandstone
Cores,
J. Id
R.M., and
20. Raiders,
R.A.,
m,
tive

pmented

Biotechnology,
New Orleans,
H. M., and Coeterton, J.W.:

Enhanced

Gil

and D@

of Microbial
Plugsing
in
(19s6)
1, 195-203.
M.J.: Microbial
34ec-

JzTcrobiol.
McJnaney,
RecoveY,

J.

Id.

Microbiol.

fMay

3,215-30.

.. .

??_?A

4. Fitch, J.P. and Canfidd,

C.M.:
-Field Performance
Evaluation
of
Cmslinkd
PoIymem To lncma.!z Git P.emvery in tie Witmi@m
Field,
california,
paper SP!3 5366 pre$ded
at tie 1975 SPE California
Regioml
Meeting,
Venhma,
April Z-t.
5. Bolton, H.P. etal.: Setecdon
of Polymers for the Con~ol of MobiJity and Peqwabw
Variadon
at Riddidd
East Dome
Unit,
Orange

!31 Metric

Conversion

API

19ss)
7.

SPE

fiti,

cycles/see
dyneshmz

SPE

243-50.

S. E.: EvrdWion
R.M.
WI Samr@t,
termine Crcmlink Time of FmcMriq
Fluids,
ed at the 1987 SPE Oiliiefd and &nthermd
San AUtOUiO, Feb. 4-6.

Hedge,

Resmvoir

Bngineaing,

Novemk

1991

of FieJd Mefkods To DeSPE 16249 ~tChemisrry

Conference,

141.5/(

Cp

8893 pmsmted atti

1930 SPE catiforma Regional Meeting,
Los Angeles,
Apd
9-11.
6. Mumattah,
N.A.: Cbmmdum
(Ill) propionats
A Cmsdinking
Agent
for Wafer,Soluble
Polymers
in Hard Oitfield Brines,
SPERE
(Feb.
cm,

ft

Orl@l
dm.4,
am.

2PE
1691.
1969

131.5

+AP9

g/cm3

1.0*

E03

Pas

1 .O*

E+OO

Hz

X,

1.O*

E01

Pa

3.04S*

E01

= m
=.

E+02

(F32)/l.8

p?.i
TOvaaro

Factors

6.S94

757

kpa
SPERE

factor Is exact
rnmusmlpt
RW64

wived

for

review

Can

fermca

nmnu$a%xww

SPEAm.a176chnlc4

Oct.

1S89.

Now?Q.1w2.
and

Pww

accepted

PW(SPE
ExMM!on

Md

for

publlatlon

W3i)nmmti
b

Pa!

Mnm.la,

3-11.

489

,-

PERMEABILITY

6
Clampitt,

R.L.

MODIFICATION

and Neasert,

J. E.,

.:

BY IN-SITU
Nsthod

GELATION

USING

A NEULY DISCOVERED

SPE 1%31

BIO-POLYMER

!2. Nanda. S.K.. Kumar. R., S%ndhwani,K.L., and

for

Goyal; K.L.; Char-cterisatlon

of
8 Gale Used for
Polyacrylamine-cr+
SPE 16253, Ibid.
Water/Oil
Ratio,

ControllingFormationPermeability,U.S.
Patent No. 3,785,437(January 15, 1974).
Sparlin,D., An Evaluationof Polyacrylamides
for ReducingWater Production,SPE 5610
presentedat the 50th Annual Fall Meeting of
the SPE, Dallaa, September28-OctoberL, 1975.

Reducing

!3. Harada,

T., Mzeada, U., Fujinori,

K., and
Maeda, I.,
Production
of a Firm, Resilient
Gel-forming
Polysaccharide
by a Mutant of
Alkaligenes
faecalia
var. myxogenee 10C3, Agr.
(1966) 30, p. 196-198.
Biol. Chem.,

Mazzocchi,E.F. and Carter, K.M., Pilot

Applicationof a BlockingAgent-WeyburnUnit,
Saskatchewan,J. Pet. Tech. (September1974),
p* 973.

!4. Harada, T., Fujimori,K., Hirose, S., and

Maaada, M., Growth and b-G2ucan 10C3K
Production
by a Mutant of Alkaligenea
faecalia
var. myxogenee in Defined Medium,Agr. Biol.

Felber, B.J. and Dauben, D.L., Laboratory

Developmentof Lignoaulfonate
.Gelsfor Sweep
Improvement,Sot. Pet. Eng. J. (December
1977), p. 391*

Chem., (1966)30,

P.

764-769.

!5+ Harada, T., Miaakl, A., and Saito, H.,

Curdlan: A BecterialGel-formingb-1, 3Glucan,Arch. Biochem.Biophya.,(1968)~,
p. 292-298.

Hessert,
J.E. and Fleming, P.D., Gelled
Polymer Technologyfor Control of Water in
Injectionand ProductionWells, presentedat
Third Tertiary Oil Recovery Conference,
Wichita, April 25-26, 1979.

ExOPolYi6. Sutherland,I.W., l~Microbial

nd
aacchaririea:Control of Syntheaia
Acylation,In: MicrobialPolyeaccharideand
Polysaccharases(Berkeley,R.C.W., Gooday,
AcademicPress,
and Elwood, D.C., eda.),
~.,
New York (1979), p. 1-34.

Sandiford,B.B. and Graham, G.A., Injectionof

Polymer Solutionsin ProducingWells,
presentedat 71st NationalMeeting of AIChE,
February 20-23, 1972.

t7* Williaaa,

A.G. and Mlmpenny,

J.W.T.,
Production
by Paeudo~nae
NCIB 11264 Grown in Batch Culture,
J. Oen.
Mlcrobiol.,
(1977)
102, p. 13-21.

White, J.L., Goddard,J.K., and Phillips,H.M.,

Use of Polymers to ControlWater Productionin
Oil Wells, J. Pet. Tech. (February 1973),p.
143*

Exopolysaccharide

McInerney,H.J., Iianzie,D.E., ad
Pre-teet Studiee nd Deeign
Enhanced Oil Recovery Field
Pilot, presentedat the Eighth Tertiary011
Narch 9, 1989.
RecoveryConference,Wichita,

28. Knapp, R.U.,

Dabboua,M.K. and Elkins, L.E., Pre-injection
of Polymers to IncreaaeReservoirFlooding
Efficiency,SPE 5836 presentedat the SPE-AIME
Symposiumon ImprovedOil Recovery,Tulsa,
March 22-24, 1976.

Chiahola,
J.L.,
for a Microbially

29. Cuaack, F., NecLeod, F.A., Coeterton,J.W., nd

Lappin-Scott,H.M., FormatIonof
Ultramicrobacteriato Enhance Oil Recoveryby
SelectivePlugging,presentedat IGT Sympoalum
in Gas, Oil, and Coal Biotechnology,New
Orleans,LA, December 1988.

Fitch, J.P. and Canfield,C.M., Field

PerformanceEvaluationof CrosslinkedPolymers
to IncreaseOil Recovery in the Wilmington
Field, California,SPE 5366 presentedat the
4?th Annual CaliforniaRegionalMeeting of the
SPfi,Ventura, April 2-4, 1975.

30. MacLeod, F.A., Lsppin-Scott,H.M., and

a Model Rock
Costerton,J.W.,
System by Using Starved Bacteria,Appl.
El,viron.
Microbial.,(1988)54, p. 1365-1372.

!~plugging
Of

Bolton, H.P., Carter,W.H., Kamdar, R.S., and

Nute, A,J., Selectionof Polymersfor the
Control of Mobilityand PermeabilityVariation
at RichfieldEast Dome Unit, Orange County,
California,SPE 8893 presentedat the 50th
Annual CaliforniaRegional Meeting of the SPE,
Los Angele~, California,April 9-11, 1980.

310 Raiders,R.~., McInerney,M.J., Revua, D.E.,

Torbati,H.M., Knapp, R.M., and Jenneman,G.E.,
Selectivityand Depth of MicrobialPlugging in
Berea SandstoneCores, il.Ind. Microbial.,
(1986)~, P. 195-203+

Martin, F.D. and Konarik, F.S., ChemicalGels

for DivertingC02: BaselineExperiments,SPE
16728 presentedat 1987 SPE Annual Technical
Conferenceand Exhibition,Dallas, Texas,
September27-30, 1987.

32. Raiders,R.A., Knapp, R.M., and McInerney,

selectivePluggingand
M,.T.,lt~icr~bial
EnhancedOil Recovery,J. Ind. Microbial.,
(1989)1, p. 215-230.

Mumallah,N.A., Chromium(III) Propionate: A

Crossli,nking
Agent for Water-SolublePolymers
in Real OilfieldWaters, SPE 15906 presented
at 1987 SPE InternationalSymposiumon Oilfield
Chemistry,San Antonio,Texas, Feb. 4-6, 1987.
Hedge, R.M. and Bsranet,S.E., Evaluationof
F{eidMethodsto DetermineCrosslinkTime of
FracturingFluids,SPE 16249, Ibid.

*..
.
SPF 1Q671
,

-----------------

Table

,.

1.

----

Table 2. samples of polymer aolutiona

Characteristicsof the polymer

..

for viecoeity

meaaurementa

Volubilitycharacteristics:
NaOH
(M)

Sample
#

1. Soluble in 0.1 N (or greater) sodiumandior potassiumhydroxide.

2. Soluble in concentratedformic-and
pilosphoric
acid, and in dimethylaulfoxide.
3. Insolublein water, methanol,ethanol,
iaopropanol,and acetone.
.

S. VOSSOUGHIAND C. S. BULLER

.-.

Conversionof alkaline solutionsof polymer to

hydrogels:
1. Neutralizationby organic-or mineral
acids.

NaCl
(PPM)

Polymer
J&L

0.1

O*O

0.1

O*O

0.1

10,000

0.1

20,000

0.1

30,000

0.1

50,000

O*1

100,000

1.0

0.0

0.0

2. Neutralizationby ccrbon dioxide.

Propertiesof the hydrogel:

9

1.0

1. 98% of the weight ia accountedfor by the

entrainedwater.

10

1.0

10,000

2. Cda

11

1*O

20,000

12

1.0

30,000

13

1.0

50,000

1.0

100,000

at

remain stable
least
24 hours.

to heating

to 260F

for

3. Repeated

cycles
of dissolution
in alkali
followed
by precipitation
aa a consequence
of neutralization
do not alter
the physical
properties
of the polymer.

14

Table 3. Polymer productionin batch cultures

I
N!14C1(M)

Wet Wt. (mg/ml)

Bacteria Nydrogel

pH

Hydrogel/
Bacteria

0.005

77.0

244.5

6*6

3.17

0.010

100.0

321.9

6.?

3.21

I
I

0.015

109.0

304.0

;.2

2.79

0.020

106.0

287.5

6.9

2.71

0.025

108.5

280.5

7.2

2,59

II .0.030

38.5

38.5

4.7

O*9O

Bacteriawere grown in minimal salta medium

containing3% glucose (w/v) and the indicatea
concentrationsof ammonium salt as the nitrogen
source. Bacteriawere harveatedafter 72 h
incl}ation,
with aeration,at 30C.

103

J I I 11111
O

I I I Ifll]

I 1 I

1 1 I 11111

1 1 I 1111

1114

Samplc#e

-!
4 Sampk+9
Cl SemploJIO
X Sompk#ll
A Sompb#l2
M Somplc#l3

10

c1
I

100

I 1 I

11111

100

10

102

no.

rem behawer d polymor aduuone In 1.0 NNaOH.

l-vkcaeltyhhear

103

103

rate, c-

Shear

11111

1 11111

1114

0 Somp19#l
O Sample#2
Cl Sampl@
X Samplc#4
A Sampla#5
.

102

A
A

~o

x
0
1

~$
m

cl

:a

1-

100

1 I I 11111

fo 0

1 1 I 11111

10

102

Shear rate,

Fig, 2-Vlecoelty/$hear

1 I 1 Ill

103

s-

mw behavior of polvmer eolutlono In 0.1N NeOH.

20

 ,.

WE 19631

$.

103

10 f

~~1

100

1111111

100

10

Ill

102

103

Shear rate, s-

F@.3-Shaar aanaklw behavkxo fpolymaraolutb nfiamp let

Time,

Fig. 4-Steady atmr

v16c061(Y moawamonto
67

minutes

of tho gal v-. thno.

10

. .

I II

I L

%
$
$

$?03
J
m
~
g
:7

102
10-

1 1 II

to 0
Shear rate
FIG. S-!&hear

etrw2/ehoer

10
, S-l

ret. bdavtor

et the gd.

10-

100
Frequency,

10
Hz

FIG.6-Stotago modulus moa.urementa

of tho gel,

-,
.

104

lqbi
10

II

&
.%
m
o

-to

1 1 I

10-

Vi-

Hz

meeeurernente

Of the wit

10

100

F@. 7-DyMmko

II

Frequency,

80

0,06

Legends:
0Pressure Drop
UFlow Rate

0.05

Brine
Injection

0.04 ~

d+--------+
.~%:+
\
-*-4
t
Sodium f@roxlde

\
4n,

.>,

v
~ater
1

\
s

Breakthrough

\
\\\

\
\
\

I
12:00

13:00

0.01
Fbw

Stopfxd
I

Acid
lnj4

15:00

bdlum Hydroxide
Inj+lon

1600

17:00

I
18:00

Fbw
Rosumad

19:00 20:00

21:00

Clock Time, hr. (Day 1)

Fig, 8-Llnoar

#
s
ii

Broaktlwough

Breakl~rough

14:00

0,02

!I

t
Blopo~mo;\~4
Injectbn

lr&!on

8
0.03 ~

coreflood

test for In.dtu

M

gelation,

Day 1,

Fbw Stopped n
Loft to Soak for
10 hours

Fbw
Roaumad

22:00

23:00

0.00

I
24.00

100

,
<

~?i

..,.

<.

WE 19631

II
!
It

(0)

Isd do~a

WISS~Jd