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Chemical Enhancement of Oil Production

by Cyclic Steam Injection


Charles M. Blair J r., SPE. Magna Corp.
Richard E. Scribner, Magna Corp.
Charles A. Stout, SPE. Magna Corp.

Summary
Members of a special class of interfacially active
chemicals were injected into wells in Kern County, CA,
immediately before and during the huff 'n' puff steaming
cycle. The chemical treatment was found to give significant increases in oil production.

Introduction
Earlier work in this laboratory and in the field 1,2 indicated that injection of water-soluble demulsifiers into
the steam used in cyclic steam stimulation operations
often gave improved oil production. This work extends
this earlier application to the use of a broader range of
compounds that we call thin film spreading agents
(TFSA) and that, while still acting to prevent emulsification, are found to aid in oil displacement and waterwetting of rock surfaces. 3 These compositions frequently have higher oil solubilities and higher oil/water
distribution ratios than the formerly used products.

Mechanism of TFSA Action


Asphaltic or other semi polar constituents of petroleum
adsorb rapidly at oil/water interfaces to form thick,
viscous films that stabilize water-in-oil emulsions.
Although the spreading pressures of these films are
typically in the range of 15 to 30 dyne/cm (15 to 30
mN/m) and thus leave very substantial oil/water interfacial surface energies [25 to 40 dyne/cm (25 to 40
mN/m)] after adsorption,4 they create potential energy
barriers that prevent coalescence of water droplets.
TFSA compounds appear to destabilize emulsions by
adsorbing at the oil/water interface, spreading somewhat
01492136182101210700$00.25
Copyright 1982 Society of Petroleum Engineers of AIME

DECEMBER 1982

more strongly than the asphaltic stabilizing agent and


pushing it back into solution in the oil. Fig. 1 shows the
relationships between spreading pressures and concentration for each of the two TFSA compounds used in this
study when spread at interfaces between refined mineral
oil and water. In these graphs, the concentration is expressed as the thickness of the TFSA film, with the
assumption that all added material is adsorbed at the interface. The procedure of Ref. 4 was used for these
measurements. The spreading pressure of TFSA rises
rapidly with concentration, reaching pressures sufficient
to displace asphaltenes back into oil solution at maximum thicknesses of about 4 to loA -around the
diameter of a water molecule. TFSA lie flat at the interface, forming thin, mobile films that present almost no
barrier to close approach of water droplets. This allows
coalescence of water droplets and separation of oil and
water into bulk phases.
A further important property of a properly designed
compound is that its spreading pressure reaches a limit as
its concentration in the system increases or as the interfacial area decreases. TFSA in slight excess of that required to displace a hydrophobic interfacial film by a
very thin, hydrophilic one appears to be dissolved in the
oil phase, leaving an interfacial tension (1FT) in the
range of 10 to 20 dyne/cm (10 to 20 mN/m) and a
residual thermodynamic incentive for coalescence.
In these respects as well as others, TFSA compounds
differ sharply from ordinary surfactants and micelleforming amphipathic agents. These latter agents generally undergo close packing at interfaces, forming thicker
films and producing low 1FT's.
There is strong evidence indicating that the adsorption
2757

TABLE 1-DATA ON WELLS TREATED

Well
-

Field

Producing
Formation

MS
MS
MS
MS
MS
MS
MS
MS
MS
MS
MS
KF
KF
KF
KF

Potter
Potter
Potter
Spellacy
Spellacy
Spellacy
Spellacy
Speilacy
Spellacy
Spellacy
Spellacy
Chanac
Chanac
Chanac
Chanac

--

F148
F200
G99
R277
R437
R517
R557
R677
R787
R977
R1087
Y48R
Y70
Y72
Y87

(tt)

Producing
Interval
(tt)

1,400
1,500
1,028
1,158
1,255
1,130
1,172
1,100
1,072
1,600
875
2,017
2,028
2,012
2,067

285
200
203
99
176
78
75
90
100
120
107
210
280
321
240

Approximate
Depth

Steam Injected
(bbl of water)
Without TFSA

With TFSA

10,161
7,509
9,400
14,160
12,590
9,756
4,163
12,082
11,004
9,257
10,326

9,220
9,800
9,690
10,000
10,251
11,930
10,985
12,780
12,618
11,582
10,847
13,590
15,490
11,390
13,114

12,480

Steam Quality
(%)
Without TFSA
With TFSA
62
68
65
62
66
63
58
71
69
60
71
60'
60'
60'
60'

61
59
65
70
62
65
55
66

'Estimated.

60

-------i' Oil-WATER
:I

40

INTERFACIAl.. TENSION

50

~
Z

>

ow

40

J>----- _----D-----------.-----------ji

.......

20

~
w

g:

LTFSA_t

~"o''''
/

r'/

10

til

... , ..... ."

-'

30

oa::

Q.

...J

(5

" ,"

20

1+:::'"

...J

~
o

iii
w
a::

oR

I~
.,~
~~~~_~-o
j.-----

"

0'

10

",.,

""

/'
0 - - - - 0 UNTREATED FLOOD WATER
-- -_ _ THERMOFLOOD 805 IN FLOOD WATER

THICKNESS OF INTERFACIAL FILM, MICRONS x 10'

PORE

VOLUMES OF AQUEOUS PHASE INJECTED

Fig. 1-Spreading pressures of TFSA at oil/water interface.

Fig. 2-Effect of TFSA on residual oil production in laboratory


flood with MS crude oil.

of thick, hydrophobic films from crude oil is not limited


to water surfaces but also occurs at other high-energy
surfaces such as those of reservoir rocks. Such surfaces,
while often described as preferentially water-wet, may
be so only with respect to refined hydrocarbons containing no oil-soluble, surface-active constituents. In actual
crude oil reservoirs, probably much of the rock surface is
in contact with oil and becomes at least partially oil-wet
or emulsified by an adsorbed thick, viscous,
hydrophobic film derived from the oil. As a result, condensate introduced by steaming or water introduced during waterflooding displaces only the more mobile core
volumes of oil. Perhaps the problem of oil removal is
partially one of causing coalescence of rock with water,
leading to displacement of oil from the surface.
It seems likely that TFSA compound, if present in the
reservoir, should aid this coalescence or water-wetting
process. Also, since properly selected TFSA compounds
tend not to remain adsorbed between high-energy phases
such as water and rock, they should desorb as oil is
displaced and be carried along in the oil, in which they
are preferentially soluble, to be reused in further
displacement of oil-wetting films on the rock.

To explore this possibility, laboratory sandpack cores


containing oil remaining after flooding with 1 PV of
water were flooded further in a manner similar to that of
Csaszar,s with and without the addition of TFSA to the
water. Fig. 2 shows the results of such tests with
Midway-Sunset (MS) field crude oil. Thermoflood-805, a commercial solution of TFSA-I (described
in the next section), when added to the flood water to
provide 160 ppm ofTFSA, gives increases in residual oil
production of from about 30 to 40 %, results that support
the proposed oil displacement mechanism.

2758

TFSA Selection and Application


On the basis of laboratory flooding results and
demulsification tests 6 with the appropriate crude oils,
two TFSA compounds were selected for field testing.
TFSA-I is an oxyalkylated substituted phenolaldehyde
resin of relatively high molecular weight. It was
prepared as described by DeGroote and Keiser 7 in their
Example F.
TFSA-2 is an oxyalkylated substituted phenolaldehyde
resin having an intermediate molecular weight and
somewhat greater oil solubility than TFSA-I. It was
JOURNAL OF PETROLEUM TECHNOLOGY

3BBBr--------------------------,

4BBB'r--------------------------,

.J

II
II

MS-G99
CYCLE 2

KF-Y87
CYCLE 5=

IU

JSBBBr--------------------------.

16BBBr - - - - - - - - - - - - - - - - - - - - - - - - - ,

o
o
I[

D.
.J

MS-F148
CYCLE 11

MS-F2BB
CYCLE 2
B'~~----------------------_2

MONTHS

ON

1
PRO~UCTION

Fig. 3-0il production volumes before and after use of Thermoflood-803 in steam.

6BBBr-----------------~~-----,

4BBBr--------------------------,

.J

II
II

-I-

steam only
MS-R 1.087

CYCLE 3

S'77

CYCLE 7
B

J 6BBBr--------------------------,

4BBBr---------------------~---,

I[

D.
4--

.J

steam only

t"1S-R277

t-1S-RSJ.7

CYCLE 8

CYCLE 9

12

M 0 N TH S

ON

PRODUCTION

Fig. 4-0il production volumes before and after use of Thermoflood-805 in steam.

prepared as described by Blair 3 in his Example II but


modified by use of 40 % of the amount of alkylene oxide
called for in the example.
Since these compounds have very low solubility in hot
water, we compounded them for use as waterdispersible, homogeneous micellar solutions by following the directions of Blair. 8 Commercial test products
Thermoflood-801 and -805 contained TFSA-l.
Thermoflood-803 contained TFSA-2.
Since it seemed likely that less TFSA would be required in field applications than in the laboratory because
of more opportunity for diffusion and reuse of chemical
in the larger-scale operations, we decided to use one-half
the laboratory quantity, or 80 ppm, on the basis of the
volume of condensate introduced during the steaming
DECEMBER 1982

period. This concentration of TFSA corresponds to 250


ppm of the commercial Thermoflood formulation.
Table 1 lists the wells treated, the amount of steam injected, and other well data. Both the MS and Kern Front
(KF) fields produce oils having API gravity in the range
of 13 to 14 [a density of 0.973 to 0.979 g/cm 3 at 60 OF
(15.6q]. The program for the majority of wells called
for injection of about 10,000 bbl (1590 m 3 ) of water as
wet steam, although the actual volumes injected ranged
from about 9,000 to 15,000 bbl (1430 to 2390 m 3 ). The
final chemical treating program adopted was as follows.
1. Mix 55 gal (0.21 m 3 ) of Thermoflood reagent with
water and drop it in the hole. Use enough water to provide a solution with three times the volume required to
cover the perforations.
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6BBB~-------------------------.

4BBBr--------------------------.

oJ

..ou

steam... onIYMS_R437

MS-R557

e 1-~~~======::::~~L:E~6~-1
12

~8BBBr--------------------------.

o
o

CYCLE 7

4000r--------------------------,

IE
Do
oJ

steam only

CYCLE 1B

CYCLE 6

~-----------R~S-R787

MONTHS

MS-R677.

ON

PROOUCTION

Fig. 5-0il production volumes before and after use of Thermoflood-805 in steam.

4BBB~--------------------~---.

oJ

m
m
2

.u

hsteam only

KF-Y48R

I-<F- 'T'70

CYCLE

CYCLE 5"

B~------------------~----~12

o
o

:12

"~.O""

IE

"+

Do
oJ

o
VF-'T'72

CYCLE 5

MONTHS

ON

12

PRODUCTION

Fig. 6-0il production volumes before and after use of Thermoflood-801 in steam.

2. Start steam injection and introduce Thennoflood


continuously into the steam line at the wellhead or
downstream from the regulator at a rate calculated to introduce another 55 gal (0.21 m 3 ) of Thennoflood during
the anticipated steaming period.
Well selections and data collection for this study were
done by personnel of the lease operating companies. Our
research personnel observed the preparation and application of the chemical solution placed in the hole and
monitored the injection of chemical into the steam line.
Occasional spot checks by research personnel found no
important errors, but the data are subject to the scatter
and uncertainty nonnally associated with field operations, and all events that might have affected results may
not have been recorded.
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Results and Discussion


Of the 11 wells in the MS field treated with either
Thennoflood-803 (Fig. 3) or -805 (Figs. 4 and 5), 9, or
82 %, showed substantial increases in oil production.
The individual well data presented in the figures allow
for each well the calculation of ratio of last cycle production with TFSA to next-to-last cycle production with
steam alone. The mean of well production ratios was
4.53, with a standard deviation (SD) of 4.10. The ratio
of total volumes of oil produced by these same wells during the two cycles described came to 2.49. This latter
ratio is the mean of well production ratios weighted by
untreated well production volumes. The ratio of total
volume of oil produced to volume of water (as steam) inJOURNAL OF PETROLEUM TECHNOLOGY

TABLE 2-RATIO OF PRODUCTION OF WELLS TREATED WITH TFSA


TO PRODUCTION WITH STEAM ONLY
Effective
Same Cycle'

Observed Cycle
to Preceding Cycle

Field

Number
of Wells

Mean
Well Ratio

VolumeWeighted
Ratio

Mean
Well Ratio

VolumeWeighted
Ratio

MS
KF
combined

11
4
15

4.53
1.41
3.70

2.49
1.30
2.19

6.47
2.01
5.28

3.56
1.86
3.13

Based on 30% average cycletocycle decline rate.

TABLE 3-COST-BENEFIT ANALYSIS OF TFSA USE


Production, next-to-Iast cycle, steam only, bbl
Expected production in last cycle (based on 30% decline), bbl
Actual production in last cycle with TFSA, bbl

34,296
24,007
75,058

Incremental production with TFSA, bbl

51,051

Value of incremental production, at $22/bbl, U.S. dollars


Cost of TFSA used, U.S. dollars

1,123,122
24,750

Net increase in revenue in last cycle with TFSA, U.S. dollars


New increase in revenue per well with TFSA, U.S. dollars

1,098,372
73,225

jected was 0.535 for the last cycle with TFSA compared
with 0.233 for the preceding cycle with steam alone.
Of the 4 wells in the KF field treated with either
Thermoflood-801 (Fig. 6) or -803 (Fig. 3), 3 had
substantial increases in production ratio, and 1 had a
reduction. The mean well production ratio was 1.41,
with an SD of 0.57. The volume-weighted mean ratio
was 1.30. Fig. 7 shows the cumulative oil production for
the entire 15 wells during the last cycle with TFSA and
during the preceding cycle with steam alone.
The preceding individual well and total production
ratios understate the benefits of TFSA use because they
compare last-cycle results of using the chemical agent to
next-to-Iast cycle results of using steam alone. Studies of
cyclic steam production in other fields including Huntington Beach 9 and Duri 10 show average cycle-to-cycle
decline rates well above 30%. From the decline rate we
can estimate the expected, last-cycle, steam-only production volume from the observed production during the
next-to-Iast cycle. This, in tum, permits estimation of effective, same-cycle production ratios resulting from
TFSA use.
Table 2 presents the effective, same-cycle production
ratios for the various well groups calculated on the basis
of a conservative 30% decline rate. Also shown for the
same groups are the observed ratios oflast-cycle production with TFSA to next-to-Iast cycle production with
steam alone.
Table 3 gives a simplified analysis of the economic
benefit of TFSA use. This does not take into account the
greater present value of the production resulting from
higher production rates.

Conclusions
The use of properly selected TFSA compounds with the
steam injected in huff 'n' puff operations leads to large
DECEMBER 1982

increases in oil production per cycle, per unit of time,


and per unit volume of water injected as steam. Results
appear to be better in the MS field than in the KF field,
although both show strongly positive responses.
From this limited number of tests, no firm conclusions
can be drawn about the relative effectiveness of the three
Thermoflood formulas tried. However, there is in the
data a persistent suggestion that Thermoflood-803 (containing TFSA-2) is the more effective of the two formulas used in the MS field.
Further work is needed to define more precisely the
relationships between chemical composition, concentration, and application method, and the extent of improvement in oil production.

Acknowledgment
We thank Ronald G. Sampson for important help in data
processing and computer graphics generation.
8BBBB~----------------------~

o
T

ste.1m only

oJ

ID
ID

1
MDNTHS

DN

PRDDUCTIDN

Fig. 7-Cumulative oil production of all wells before and after


use of TFSA in steam.

2761

References
1. Muggee, F.D.: "Process for Recovery of Petroleum by Steam
Stimulation," U.S. Patent No. 3,396,792 (1968).
2. Rohiback, G.: "New Additive Promises Revised SteamStimulation Economics," Oil and Gas 1. (Oct. 10, 1966) 207-09.
3. Blair, C.M. Jr.: "Method of Recovering Petroleum From a
Subterranean Reservoir," U.S. Patent No. 4,260,019 (1981).
4. Blair, C.M. Jr.: "Interfacial Films Affecting the Stability of
Petroleum Emulsions," Chern. and Ind. (May 1960) 538-44.
5. Csaszar, A.K.: "Solvent-Waterflood Oil Recovery Process,"
U.S. Patent No. 3,163,214 (1964).
6. Treating Oil Field Emulsions, C.F. Kruse (ed.), API and
Petroleum Extension Service, U. of Texas, Austin (1974) 33-45.
7. DeGroote, M. and Keiser, B.: "Process for Breaking Petroleum
Emulsions," U.S. Patent No. 2,557,081 (1951).
8. Blair, C.M. Jr.: "Micellar Solutions of Thin Film Spreading
Agents," U.S. Patent Nos. 4,309,306 and 4,326,985 (1982).
9. Adams, R.H. and Khan, A.M.: "Cyclic Steam Injection Project
Performance Analysis and Some Results of a Continuous Steam

2762

Displacement Pilot," 1. Pet. Tech. (Jan. 1969) 95-100; Trans.,


AIME,246.
10. Atmosudiro, H.W.: "Steam Soak Increases Recovery in Indonesia," Oil and Gas 1. (Aug. I, 1977) 104-108.

SI Metric Conversion Factors


bbl x 1.589 873
dyne/em X 1.0*
ft X 3.048*
mieron X 1.0*
Conversion factor is exact.

E-Ol
E+OO
E-Ol

m3
mN/m
m
J.tm

JPT

Original manuscript received in Society of Petroleum Engineers office Feb. 10, 1982.
Paper accepted for publication July 30,1982. Revised manuscript received Oct. 12,
1982. Paper (SPE 10700) first presented at the 1982 SPEIDOE Joint Enhanced Oil
Recovery Symposium held in Tulsa April 4-7.

JOURNAL OF PETROLEUM TECHNOLOGY