Chemical Methods for Shutting Off Water

Wells
By H. T.

III

Oil and Gas

KENNEDY*

(New York Meeting, February, 1936)

THE fact that intrusion of water into oil wells can be prevented by
treating the sand adjacent to the well seems to have been only recently
recognized. Swan l mentions the process of solidifying naphthalene in
strata. R. Van A. Mills 2 recommends the use of materials such as
sodium silicate and sodium carbonate, which react with oil-field water to
form solid plugging agents.
When a well is drilled in a new field the oil sands are found essentially
devoid of water (Fig. 1). Unless a completely impermeable break exists

FIG. 1.-WATER

CONDITION:> WHEN FIELD IS DRILLED.

over wide areas in the field, no water is found above the lower limit of the
oil zone and no oil is found below the upper limit of the water zone.
After considerable oil has bepn takC'n from the well, however, it is almost
universal experience that water intrusion occurs. This intrusion may be
of two kinds. The water may follow a path parallel to the bedding
planes of the producing formation through loose streaks in the pay sand,
as shown in Fig. 2, or the water level of the field may rise and enter the
well by coning (Fig. 3). Water entering from the side is called" edge
water," and that coming in from the hottom is called "bottom water."
Effectiveness of any method for shutting off water depends not
ollly Oil thl' effpe(.ivp tJ'(~atm(,lIt or t.he Hand adju('PIlt. to the well but 011
Manllscript ('e('ei\'pd at tl,c office of the In:>titlltc March 19, 193fi.
& Dc\'elopment Corporation, Pittshurgh, Pa.
I U.S. Patent 1379657 (1921).
2 U.S. Patent 1421706 (1922).
177

* Gulf Research

178

CHEMICAL METHODS FOR SHUTTING OFF WATER IN OIL AND GAS WELLS

the geologic conditions of the sand. It is possible, of course, that oil

and water, or gas and water, may enter the well through the same sand,
although probably this is not a frequent occurrence. If this occurs, it is
obviously impossible to shut off water without at the same time shutting
off the flow of 011 or gas, and no method of sand-treating can be effective.

FIG.

2.-CONDITION AFTER EDGE WATER IS ENCOUNTERED.

Edge water can be completely shut off without in any way interfering
with the flow of oil or gas. As a matter of fact, the flow of these fluids
may be substantially increased by water shutoff, provided that essentially
impermeable layers exist between the water-bearing strata and the strata
bearing gas or oil, or that the vertical permeability of the sand is low
compared to the horizontal permeability of the loose streaks.
The efficiency of any process for shutting off bottom water depends
largely on the uniformity of the sand horizontally and vertically. The
I

WELL

OIL

WATER'

----=------ ----------i-------------=----I

'77777777777777777777777/777777/ /,
FIG.

3.-CONING OF BOTTOM WATER.

mOiOt unfavorable condition would be a perfectly homogpneouti sand without "hale breakiO or otllf~r barrierti. No sand of thiti nature has ever been
found, but the couditioll may he approaehed ill salldiO ill whieh the iOhale
breakiO occur over very small areas, iOO that water may rise vertically
between the breaks not far from the well. Even in these unfavorable

H. T. KENNEDY

179

conditiom~, however, considerablr- reduction in water, or increase in

amount of oil without wat.er, can be acnompliKhed. On theoretical
grounds Muskat and Wyckoff have calculated that a disk 5 ft. in radius
at the bottom of a well will increase the permissible oil production,
without water, by about 40 per cent. If productive streaks of sand are
separated by impermeable breaks, bottom water may be entirely eliminated by simply plugging with cement or lead wool, but these bottom
plugs can bfnlsed only at the bottom of a well, and often pay sands exist
below this level from which oil could be obtained by the use of chemical
water shutoff, and deeper drilling.
Chemical water shutoff, as described in this paper, involves the formation of a precipitate in the pores of the water-bearing strata, by the use of
chemicals that may be precipitated in water-bearing strata without at the
same time affecti.ng oil or gas-bearing strata. The effectiveness of a water
shutoff treatment depends upon the amount of precipitate that can be
formed in the porr-s, and upon the nature, especially the hardness, of the
precipitate. If precipitating solutions are injected into both oil and
water strata it is evident that precipitation must be avoided in the former,
and in selective shutoff only one solution must be required, since in
a method using two solutions injection and precipitation into both strata
cannot be avoided. In this case, therefore, we are limited to the use of
chemicals that will precipitate in contact with natural oil-field waters.
The bulk of the dissolved constituents in most water consists of
sodium chloride, which cannot be precipitated by any ordinary reaction
because salts containing sodium are all soluble in water, and because there
is no commercial material that can be added to precipitate an insoluble
chloride. The precipitable compounds of oil-field brines are thus limited
to calcium and magnesium salts, which occur only in small amounts,
seldom more than 1 or 2 per cent by weight. However, several materials
are known which form voluminous precipitates on contact with water
itself, and in which the volume of the precipitate is limited only by the
amount of water available to react; among them, antimony trichloride,
which in contact with water forms a voluminous precipitate of antimony
oxychlorides. This material may be injected either in a concentrated
water solution or dissolved in oil.
Silicon tetrachloride also reacts with water to form a voluminous
precipitate of silicic acid, which in addition forms an effective cementing
material to consolidate and strengthen the sand in the walls of the well.
There are several other materials that may be advantageously used,
such as superfatted soaps, finely divided cements made up in nonaqueous
suspensions, and colloidal solutions which on dilution or contact with salt
water are precipitated, and form precipitates many times larger than may
be obtained by any reaction involving chemicals dissolved in oilfield water.

180

CHEMICAL METHODS FOR SHUTTING OFF WATER IN OIL AND GAS WELLS

Th()s~~ llOt. ill dil'f~d, (ont.ad, wit.h t.lw wat.er ('ondit,jolls ill\'olvpr! ill
oil production will no doubt. be surprised to learn that more water than oil
is produced by the oil wells in the United States. As a matter of fact, for
the 1,000,000,000 bb1. of oil, we annually produce about 2,200,000,000 bb1.
of water. The lifting cost at 10 per barrel amounts to $220,000,000, a
large part of which is avoidable. Table 1 shows the water-oil ratios for
wells in different fields. This does not include water produced in gas
TABLE

l.-Water-oil Ratios in Oil Wells

Water to Oil Ratios

Locality

Gulf Coast ............... '" ................

Texas (exclusive of Gulf Coast) ................
Louisiana and Arkansas .......................
Mid-Continent (Kansas, Oklahoma, N. Mexico).
Grand average .............................

Pumping

Flowing

Total

4.1
3.2
14.3
2.4

0.13
2.4

0.9
2.7
14.3
2.1
----

0.1
2.2

wells, the lifting for which, per barrel, is much higher, since pumps must
be installed for the sole purpose of lifting water. The elimination of the
lifting expense is not the only advantage to be gained by shutting it off.
When a nearly perfect shutoff can be obtained emulsion troubles and
consequent expense of treating emulsions can be eliminated. Oil
production and oil recovery per acre may be substantially increased by the
utilization of the driving force of water, which in many cases is the
primary source of energy in forcing oil from sand. In competitive fields
many wells are found in which the daily production is limited by the
capacity of the pump, and the water that is produced decreases the oil
production by an equal amount. Also, many wells are abandoned
because the lifting cost of water and oil cannot be paid for by the oil
production. Often wells produce 95 to 99 per cent water, and the
expense of handling the water rather than the shortage of oil production
leads to their abandonment.
Perhaps one of the most important applications of chemical water
shutoff is in the saving of casing expense, especially in cable-tool drilli~g.
Many casings are set for the sole purpose of preventing intrusion of water
into the hole while drilling but frequently this function can be performed
by an inexpensive treatment of the water sand by the proper application
of the methods here deHcrihed, ami one OJ' mOf(~ Rtrings of cal'ing may ))p.
Haved on each well.
The method of injecting ('hemieall' into saud naturally variel' with
the condition of the well and equipment available. For a well pumping
with fluid level substantially at the bottom, it is convenient to injeet the

H. '1'.

KENNl<~IH

J:O;1

ehclllieal through thc eatlillg without ditlturbing thc pumpillg eq uipmcnt,

except to pack off the polished rod. It is desirable to remove all water
from the hole by continuing to pump with standing valve set practically
on bottom while 10 or 15 bbl. of oil are injected into the casing. This
procedure allows the water to be removed without coming in contact
with the chemical charge. If the chemical is soluble in oil, such as

FIG.

FIG.

4.-EQUIPMENT FOR INJECTION OF CHEMICAL.

5.-WELL-HEAD CONNECTIONS FOR CHEMICAL INJECTION.

antimony trichloride or silicon tetrachloride, it is best to employ the oil

solution directly following the oil, the amount to be used being determined
by the thickness of sand to be shut off and the depth to which it is desired
to penetrate. Experiments have shown that 1000 lb. of either of these
chemicals is ample for 20 to 30 ft. of average sand, although it is evident
that very loose sands require more than tight sands; also, that a chemical

182

CHEMICAL METHODS FOR SHUTTING OFF WATER IN OIL AND GAS WELLS

like silicon tetrachloride, which forms a hard, voluminous precipitate,

can be used more sparingly with good results than materials that are less
effective for the purpose. After the chemical is pumped into the casing it
is general procedure to apply an oil load, to make sure that the chemical is
forced from thl' wrll into the sane\. Fig. 4 HhowH the equipmrnt used in

FIG.

(i.-OOUBLE-PACKER .\IETHOlJ OF INJECTING CHE~IlCAL.

mixing the chemical and pumping it into the well, and Fig. 5 showH the
well-head connections on a well in the Seminole area to which this process
was applied.
Although silicon tetrachloride and other ehl'micals of thiR elass do
not react in the absence of water, and therefore would do no harm to an oil
sand, it is sometimes convenient, in order to avoid waRtl' of ehl'mical, to

FIG.

7.-INJECTION OF CHEMICAL THROUGH PERFORATED CASING.

employ the double-packer method of treating sand (Fig. 6). This

is done by setting an anchor packer near the top of the sand to be treated,
and a hook-wall packer just below on tubing closed at the bottom and
perforated between the packers. Water present in the tubing may be
displaced by oil ahead of the ehemieal chargp in order to avoid precipitates
of the chemical ill the well. ThiH nwthod haH diHtinet advantages of
economy of material, especially where the oil Hand iH more permeable
than the water sand or where the pressure of the latter is high.

183

H. T. KENNEDY

10

8-lO.-EQUIPMENT AND CONNECTIONS FOR CHEMICAL INJECTION ON A WELL IN

CRESCENT FIELD, OKLAHOMA.

184

CHEMICAL METHODS FOR SHUTTING OFF WATER IN OIL AND GAS WELLS

Fig. 7 HhowH the applieatiol1 of water Rhutoff method to It salld

behind a Htring of eaHing, where the eaHing Hllat may be imperfed and thUH
cause leakage into the well, or where entry of water from one sand into
another behind the casing is undesirable. Perforation of the casing can
be conveniently accomplished by either a knife or a gun perforater.
When the fluid in the well cannot be pumped down to bottom, the
injection of chemicals without mixing with water is somewhat more
difficult, but can still be applied. Oil is pumped down the casing and up
through tubing until returns of clear oil are obtained, the velocity of flow
being great enough to carry the water up the tubing. The direction of
flow is then reversed, the chemical being pumped down through the
tubing until it reaches bottom. The casinghead is closed and sufficient
pressure is applied through the tubing to accomplish the injection.
Figs. 8, 9 and 10 show the equipment and connections used for the
purpose on a well in the Crescent field, Oklahoma.
Regarding the effectiveness of water shutoff treatments, it is evident
that sand conditions have an important bearing. If water enters a well
through cracks and crevices, only materials that set up to very firm
cements can be effective, but if water enters the porous sand, as usually
occurs, a perfect shutoff of water can be accomplished. One well making
25 bbl. of water per day before treatment was allowed to stand for five
days after treatment without making a measurable quantity of water.
In other wells shutoffs better than 99.5 per cent effective have been
accomplished. A gas well in Pennsylvania was making 1000 gal. of water
per day before treatment. The second month after treatment this well
averaged 2)-2 gal. per day, which indicates that water shutoff by this
method is both effective and permanent.
ACKNOWLEDGMENTS

It is a pleasure to acknowledge my indebtedness to Dr. Paul D. Foote,

Vice President and Director of the Gulf Research & Development Corporation, for encouragement in this work and permission to publish this
paper; to Dr. B. B. Wescott; to Dr. W. P. Rand; to the Petroleum
Engineering Departments of the Houston and Tulsa Production Divisions of the Gulf Oil Corporation of Pennsylvania; and to Mr. D. E. Conaway, of the United Natural Gas Co., for assistance in development Qf
field technique in treating oil and gas wells.

DISCUSSION
(T. V. Moore pre.,iding)

B. B. Cox, * New York, N.Y.-If it is necessary to shut off a flow of gas and water
hcfore oil is encountered in a horing, would it be necessary to use oil as the solvent of
silicon tetrachloride or antimony trichloride to get the charge into the bore?

* Producing Department, Socony-Vacullm Oil Co.

185

DISCUSSION

H. T. KENNEDY.-The antimony trichloride has a peculiar property of being

perfectly soluble with small amounts of water and, as diluted, becomes totally insoluble
to form the oxychlorides. So that with antimony trichloride either water or oil
can be used.
B. B. Cox.-I gathered from your paper that antimony trichloride did not form
a hard precipitate that would support a friable sand. Therefore, as I understand
it, it would seem necessary, in shutting off a heaving water-bearing sand, to inject
a charge of oil in which silicon tetrachloride is dissolved.
H. T. KENNEDY.-The silicon tetrachloride cannot be used with water. It does
not have this property of being a clear solution with only small amounts of water.
It has to be used with oil. It can be used with oil better than with antimony trichloride because it is soluble in oil proportions.
MEMBER.-What does antimony trichloride cost?
H. T. KENNEDY.-Five hundred pounds cost $80, which is small, compared with
the other cost. Silicon tetrachloride costs from 10 to 15 per pound, depending on
the quantity purchased. The cost of manufacturing this material is small and the
price undoubtedly will be lower when greater quantities are used.
MEMBER.-I understood you to say you needed to use the material you could
remove in case you made a mistake. How do you remove it?
H. T. KENNEDY.-I neglected to mention that with silicon tetrachloride you
simply treat it with a caustic soda solution, provided, of course, you can get it in the
sand. If you cannot get it in the sand or if it goes in very slowly, that may be a long
job. Antimony trichloride forms the oxychlorides that may be removed by hydrochloric acid.
MEMBER.-When the well is treated with silicon tetrachloride and it reacts with
water, it must generate hydrochloric acid. Would that not react in the casing seats
and cause trouble?
H. T. KENNEDy.-Ordinarily it does not cause much trouble. As you probably
know, a great many wells have been treated with much larger and much more concentrated shots of hydrochloric acid without an inhibitor. Of course, acid is not
formed until the water is reached. That is one of the reasons we like to take the
water out of the well in addition to plugging the well, but there is always some acid.
If it is not absolutely 100 per cent shut off at first, there is some of the acid that
comes back. But there is very little trouble from it because the amount of acid
involved is really rather small. We get some pitting of valves, but at most it means
the replacement of the valve.
MEMBER.-Does the silicon tetrachloride precipitate in an oil sand if there is
no water?
H. T. KENNEDy.-No, only by action of the water.
SiCI.

+ 3H 0
2

= H 2Si0 3

The reaction is

+ 4HCI

It is only ill contact with water that silicon tetraehloride changes form.

T. V. MOORE, * HOllston, Tex.-Mr. Kennedy, do you think there is any water

in these oil sands?

* Humble Oil & Refining Co.

186

CHEMICAL METHODS FOR SHUTTING OFF WATER IN OIL AND GAS WELLS

H. T. KENNEDy.-Do you mean coming through with the oil?

T. V. MooRE.-No, I mean intimately associated with the oil in the so-called
oil sands themselves.
H. T. KENNEDy.-Probably there is a small amount. Howcver, one of the
advantages of silicon tetrachloride is that a hard precipitate is not formed with
small amounts of water. There must be an excess of water. I belicve it figures
out that about 7 or 8 per cent of water will not cause precipitation.
T. V. l\IooRE.-I believe that with the amount of work that has been done on this
problem we can look forward in a short time to being able to plug off all our wells
exactly where and how we want to plug them, by simply pumping the proper mixture
of chemicals down into the well. However, this process certainly must be used with
care. We tried it once on one of our wells in Southwest Texas and we cut the water
production of the well from 70 bbl. to 7 bbl. The only trouble was that we cut the
oil production from 30 bbl. to about two barrels.
H. H. POWER, * Tulsa, Okla.-I can go you the opposite on tbat, Mr. Moore.
One of the wells that was treated in Oklahoma did not cut water production, but
increased the oil production.
T. V. MooRE.-I said "this method." I did not mean Mr. Kennedy's method,
because it was a different method, but it had the same end in view, simply pumping
down the right sort of mixture into the well and bringing the water well back into a
nice pipe line oil well.
H. T. KENNEDy.-Perhaps I should mention that we changed the watcr-oil
ratio on one well we treated, before we had the advances we have now, from 2.2 to 0.7.
As a matter of fact, we increased the oil production substantially, probably bccause
of the mechanism I showed. If the water comes into a well without pushing oil ahead
of it, it is essentially like a piston without any piston rings. It just blows by. If
we start it off and increase pressures back where we want the pressure to push the
oil in, we would expect to increase oil production.
E. A. STEPHENSON, t Rolla, Mo.-Probably you are familiar with some of the
work done at Conroe; originally, I think, by Mr. Buck. Cement is pumped into the
water sand below the oil sand, while a high pressure is maintained on the casing.
The cement penetrates and seals the water sands at a pressure approximately half
that required to penetrate the oil sands. This method has been used very successfully. It would be difficult to remove the cement by any known means if part of the
oil sand were accidentally plugged and the production reduced; modern perforating
devices will solve this problem.
MEMBER.-What constitutes the charge?
H. T. KENNEDy.-We have used various amounts. It depends largely upon tl.1C
depth of sand we need to treat and upon the permeability of that sand. Loose sands
naturally require more than tight sands. Sometimes we have treated sands that
required only about half a drum of silicon tetrachloride. It was impossible to inject
more chemical because it had completely sealed the formation. At other times we
have used a drum. Sometimes we have used a charge of 1000 lb. of antimony trichloride, and sometimes 500 pounds.

* Chief Production Engineer, Gypsy Oil Co.

t Professor of Petroleum Engineering, Missouri School of Mines and Metallurgy.