"

ited States t 3,617,351

Patented Jan. 16, 1962
1 2
allowed to stand for 24 hours, the volume increases to
3 017 ,351 about 14 percent greater than the volume of the same
SHALE HYDRATION INHIBITORS FOR CLEAR weight of shale mixed into diesel Oil.
WATER DRILLING FLUIDS
Platho P. Scott, Jra, Duane B. Anderson, and Arthur Park, 5 A more striking demonstration can be made by casting
Tulsa, Okla, assignors to Pan American Petroleum Cor a block of the shale in cement such as calcium sulfate
poration, Tulsa, Okla, a corporation of Delaware after coating the block with plastic to prevent effects of
N0 Drawing. Filed Nov. 6, 1958, Ser. No. 772,164 the water of the cement slurry. After the cement is set,
11 Claims. (Cl. 252-85) holes are drilled in the shale block using a tri-cone roller
bit such as those normally used in drilling oil wells.
This invention relates to the drilling of wells. More Water is circulated through the bit as a drilling ?uid.
particularly, it relates to drilling operations in which a After the holes are drilled, they are ?lled with water and
fast chilling rate is obtained by the use of substantially allowed to stand. After 24 hours it will be found that the
clear, solids-free water as a drilling ?uid. . shale has sloughed into the holes and the block of shale
Many wells are now drilled in which the solids content will have expanded with such force that the cement case
of the drilling ?uid is maintained at as low a value as pos 15 around the shale block will be split apart.
sible. The principal advantages are a faster drilling rate, We have found that, if a water-soluble potassium or
increased bit life, and decreased drilling ?uid costs. One ammonium salt is added to the drilling water in an
of the disadvantages is an increased tendency of shale to amount equal to about 10 pounds of the salt per barrel of
slough off the walls of the hole and fall down the well. If water, the powdered shale will not expand in the test in
such sloughing occurs while the drill string is in the well, 20 the graduated cylinder. The shale block cast in cement
the bit may be stuck in the hole. If sloughing occurs dur will not expand and burst the case. Neither will the shale
ing a trip to change bits, the hole may ?ll up several in the presence of the potassium or ammonium salts
hundred feet with shale, which must be cleared from the slough into the holes drilled into the block of shale.
well before drilling can proceed. ' It will be apparent that the addition of a su?icient quan
Some of the shale which falls down the well is simply 25 tity of ammonium or potassium salts-to substantially clear
bit cuttings which have become lodged in enlarged sec water used in drilling wells will prevent swelling of the
tions of the hole. These are often dislodged from time shale and will, consequently, decrease the tendency of the
to time by the drilling operations. They are more fre shale to slough into the well. Accordingly, use of am
quently knocked into the hole when the bit is pulled monium and potassium salts in clear water permits clear
out of the well or is run back into the well. This action 30 water drilling operations to be extended to many areas
is not really true shale sloughing, but produces the same in which such operations are not now possible due to shale
effects. sloughing di?iculties. These salts also permit using clear
Part of the actual shale sloughing may be due to me water to drill deeper in many wells before sloughing due to
chanical stresses in the shale around the well. Much of mechanical causes requires converting to clay-containing
the shale sloughing, however, is due to penetration into drilling ?uids. .
the shale of the water used as a drilling ?uid. This water We have also found that, while use of ammonium and
soaks the shale, causing it to soften and often to swell. potassium salts in clear water offers a considerable im
The soft, swollen shale then either falls or is easily provement over use of clear water alone, the salts do not
knocked into the well. Thus, shale sloughing is seen to offer a complete solution to the problem. For example,
have two causes. One is of a mechanical nature. The if water-sensitive shale cuttings are placed in a jar with
other, the action of water on the shale, may be termed water and the jar is rolled for 18 hours, the cuttings
chemical in nature. will be found to have broken up considerably. The addi
An object of this invention is to decrease the slough tion of ammonium or potassium salts to the water does
ing of the shale into wells drilled with substantially clear not prevent this breakage. When certain amines are
water. A more speci?c object is to- decrease the softening added to the water, however, thebreakage of cuttings is
and swelling of shale due to the action of water on the greatly decreased. We believe this is due to adsorption of
shale. An additional object is to decrease the softening amines on the shale particle surfaces resulting in the for
action of water on bit cuttings so these cuttings will not mation of a hydrophobic protective ?lm around each
break apart so badly and can be more easily removed particle. This ?lm prevents soaking of the water into
from the water in the mud pits at the surface. 50 the shale particle and hence prevents softening of the
We have now found that we can substantially eliminate particle. The ammonium and potassium salts, on the
the shale sloughing due to the softening and swelling other hand, do not form a protective adsorbed ?lm.
action of water by use of a combination of three, and Thus, water containing these salts but no amines soaks
preferably four, additives in the water. A preferred into the shale particles and softens them. .The particles do
drilling ?uid contains the following ingredients in addi 55 not swell, but they do soften. The softened particles are
tion to water. ' then easily broken by mechanical action.
In a well this means that, if water containing am
Ammonium sulfate ________________ .._lbs./bbl__ 10.0 monium or potassium salts is used as a drilling ?uid, the
Intracol OA _______________________ __lb./bbl__ 0.5 shale will not swell and be pushed into the well by a
Separan 2610 __________________ __r____lb./bbl__ 0.02 swelling action. It also means, however, that the shale
Oil _____________________________ __gal./bbl_;. 0.5 will be'so-ftened so that mechanical causes, such as over
burden pressure, operation of the drill string in the well,
All the concentrations are in terms of weight or volume or the like, can more easily knock the softened shale'into
per 42-gallon barrel of water. lntracol 0A is an amide the well. '
of a fatty acid and a polyamine which has been made Since certain amines or water-soluble salts thereof can
65
more water soluble by forming the acetate salt. Separan prevent softening of the shale, we prefer to include a small
2610 is an acrylami'de polymer hydrolyte. amount of such amines in substantially clear water used
If water-sensitive shale is soaked in water, the shale as a drilling ?uid. It is true that, as water penetrates
will swell. For example, when a sample of the shale of from the well into the shale, the amine is adsorbed onto
the Labette shale series of Pennsylvanian age outcropping
70 the shale surfaces and is lost from the water in a zone
east of Tulsa,-Oklahoma, is ground to pass an 80 mesh within a few inches of the well. Sometimes all the amine
screen, agitated in water in a graduated cylinder, and is lost within the ?rst inch. This is still a considerable
 3,017,351 4
3 for purposes of convenience, are presented in the form of
advantage, however, since a strong ring of amine-coated
shale is established adjacent the well. This strong ring examples.
affords considerable mechanical protection to any soft EXAMPLE 1
ened shale behind the ring. To determine the abilities of various chemicals to de
One additional advantage of using the amines is their 5
protective action on bit cuttings. In drilling with sub crease the swelling action of hydratable shales, a sample
of Labette shale was powdered to pass an 80 mesh U.S.
stantially clear water, the bit cuttings tend to rise much
more slowly up the well than when a regular clay drilling standard sieve. Samples weighing 20 grams were im
?uid is used. This is due to the lower viscosity, gel mersed in solutions, agitated, and then allowed to set for
24 hours in graduated cylinders. The volume of the set
strength, and density of the clear water. Because of the
slower rate of rise of the cuttings, there is a much greater tled solids was then measured. The difference between
tendency to disintegrate and break down into very ?nely the volume of the shale immersed in diesel oil and the
divided material. This is objectionable, not only from volume in various solutions indicated the amount of ex
the standpoint of the geologist who studies the cuttings, pansion or swelling. Results of these tests are reported
but also to the driller who ?nds it more dif?cult to re 15 in Table A.
move ?ne particles than coarse particles from the water.
Table A
As previously noted, the amines greatly decrease the
tendency of the particles to soften and break apart. Thus, Additive
these amines tend to increase the size of bit cuttings re Test Change in Volume of
covered at the surface. 20 No. Nature
Concentra-
tion (lbs./
Shale (Percent)
We have found that additional improvement in opera bbl.)
tions can be achieved by adding a ?uid loss reducing ma
terial to the water containing the ammonium or potas 1 Diesel oil only _________ __; ___________ .. 0.
sium salt and the amine. In drilling with clear water a 3
2

Ammonium sulphat
Tap water . . . . . . _ _ . .

1. 40 +12.
. . . . . . . . _ . .. +14.

?occulating agent is ordinarily added to the water as it 25 4 .... 0 _____________ __ 2.80 +5.
5 4. 20 +2.
leaves the well and enters the settling pits to cause the 6 5. 00 +2.
bit cuttings and dispersed clays to settle rapidly to the 7-.-.. (1 111:014 +2.
8. .... Ammonium sulphate ____ _. 5. 60 +10.
bottom of the pits. The agent most commonly used for Nalcamine G30 _____ .. 1.00
this purpose is Separan 2610. This is a trade-mark of Separan ......... .. . 0.02
9- .... Ammonium sulphate 11.00 +2.
the Dow Chemical Company for an acrylamide polymer Nalcamine G30. 1.00
hydrolyte having from about 10 to 120 amide groups for Separan ______ .. 0.02
10- .-. Potassium Dichromate.... 1. 40 +14.
each carboxyl group and having a viscosity of at least 11--. .....do ___________________ .. 5.60 +2.
about 4 centipoises for a 0.5 percent by weight solution 12.... ..... o ........ ._ 20.00 -2.
l3. ... Sodium chloride.. . 4. 20 +14.
of the hydrolyte. If Separan is added to the water as it 14.- . Sodium chloride.... _ 11.00 +11.
is pumped down the well, it has been found that the rate Nalczmine G30. 1.00
V Separan. ____ ._ 0. 02
of loss of ?uid to formations being drilled can be con 15. -.. Manganese chloride 20. 00 +11
siderably decreased. This discovery is described in more 16-... Sodium chloride.-. 20.00 +7.
17. . .. Magnesium sulphate. .. 19. 00 +9.
detail and is claimed in U.S. patent application S.N. 18. ... Ammonium chloride .... ._ 20.00 +2.
715,494, ?led on February 17, 1958, by Julius P. Gallus. 19. -.. Potassium ferrocyanide._ _ 20.00 2.
20. - .. Sodium chloride ......... __ 17.00 +2.
The Separan seems to serve not only as a ?uid loss re 40 Ammonium sulphate. 17.00
ducing agent, but also produces, in combination with 21--.. Sodium chloride ......... __ 8.00 +2
Ammonium sulphate. 8.00
the ammonium or potassium salt and a certain class of 22. -.. Calcium chloride ........ .. 5.00 +2.
amines, a considerably increased protective action on Ammonium sulphate. 11.00
Nalcamine G30. . 0.50
shales contacted by water. That is, in the test previously Separan ________ .. 0, ()2
described in which shale particles are rolled in a jar with 45 23. -.. Intracol 0A.-. 0v 50 +8.
24.-.. Intracol 0A... 0. 50 +14.
water containing various additives, less of the shale parti Separan ........ __ 0.02
cles tend to break apart in the presence of the combina 25--.. Ammonium sulphate. 5. 60 +2.
Intracol .... 0. 50
tion of the three materials. A possible explanation is that Separan ...... .. 0.02
the Separan decreases the entry of water into the shale 26. ... Ammonium sulpha
Intracol 0A....
10.00
0.50
1.
particles and also assists the amine in forming a protective 50 Separan ________ ._ 0.02
coating over the particles. 27. ... Ammonium sulphate .... ..
lntracol .... _.
15.00
0.50
1.

In the well the Separan performs the same functions Separan ...... .. 0.02
on the well wall. Thus, less water penetrates through 28--.. Calcium chloride... 20.00 +9.
29.-.. Water only ....... .. .. +5 (Morrow shale).
the zone of shale coated with amine so there is decreased 30. -.. Diesel oil ......... .. 0 (Morrow shale).
volume of softened shale behind the amine-coated sec 55 31- - .. Ammonium sulpha
Intracol 0A.-.
0 (Morrow shale).

tion. In addition, the Separan further strengthens the Separan...-. .

32.-.. Water only._ ... .......... .. +25 (Cherokee shale).
amine-coated ring of shale adjacent the well. 33.... Diesel oil ............................ __ 0 (Cherokee shale).
As might be expected, the water containing rather 34- . ._ Ammonium sulphate .... .. 10.00 +8 (Cherokee shale).
ac 0.50
high concentrations of ammonium or potassium salts is Se aran ........ .. 0.02

somewhat corrosive. The amines tend to decrease the 60 .

35--.. Ammonium sulphate
Intracol 0A
10.00
0.50
1.
rate of corrosion to some extent. We have now found Separan.-. 0.02
that the ability of the amines to decrease the corrosion Diesel oil_..- . 0.5 glaili/ _
rate can be greatly enhanced by the addition of a small 36.-.. Ammonium sulphate .... ._ 10.00 1 (Test conducted
at 200 F.).
volume of mineral oil to the water containing the amine 65 Intracol 0A ......... .. 0.50
and salt. We have discovered that the oil, like the Sep Diesel oil ............ ..
Separan._.-.
0.5 gal./
.. . 0.02

aran, also assists the amine in protecting shale cuttings bbl.

from the action of water. For example, in the test in
which shale particles are rolled in the jar with water, In the table, Nalcamine G30 is a trademark of National
only about 2 percent of the shale particles broke apart 70 Aluminate Corporation for a substituted imidazoline hav
seriously when the water contained a little oil in addition ing the formula 1-(Z-aminoethyl)~2-methyl-2-imidazoline.
to the ammonium salt, amine, and Separan. Separan is Separan 2610, which has been previously
The nature, required concentration, and function of the de?ned. Intracol 0A is a trademark of Synthetic Chemi
various components of our composition can be better cals, Inc., for the acetic acid salt of the oleic acid amide of
understood by consideration of the following data which, 75 polyethylene diamine. It has multiple amine groups.

1
 3,017,351
Tests 3 to 7 and 10 to 12 indicate that the ammonium Table B
or potassium salt should be present in an amount of at
least about 3 pounds per barrel of water if shale swelling
is to be effectively decreased. Tests 8 and 9 indicate that Additive
Shale
in the presence of amines such as Nalcamine G30, how Test N 0. Recovery
ever, an even higher concentration of ammonium or 7 Concentra- (Percent)
Type tion (lbs./
potassium salt should be used. Preferably, the concen bbl.)
tration should be about 10 pounds per barrel. Tests 13,
14 and 16 demonstrate the relatively small effectiveness 13. 0
of sodium chloride in preventing the swelling of clay. 16. 2
15. 5
Tests 15, 17 and 28 show that the alkaline earth metal 25. 4
salts are not at all comparable to ammonium and potas 10 15. 3
. 15. 2
sium salts. Tests 18 and 19 demonstrate the elfectiveness . 13. 7
Separau 2610. --. . 17.2
of salts of ammonium and potassium other than the sul~ (NH4)2SO4__ 1O __________ ._
fates and dichromates. This seems to demonstrate that Separan 2610. -.- .02 16. 5
K01. 10 __________ - -
the action is due to the cation of the salt. Thus, it would 0. 25 30. 6
seem that any water-soluble potassium or ammonium 0. 5O 54. l
1. 00 78. 7
salt can be used. In his connection the term water-soluble 0. 25 14. 7
salt means one which is soluble at least to the extent of 0. 5O 66. 6
1. 0O 80. 4
the minimum concentration of 3 pounds per barrel of 1. 00 71. 6
water. 2. 00 78. 0
1. O0 76. 5
We belive the explanation to be that the volumes of the 1. 00 68. 4
hydrated ammonium and potassium ions are consider 1. 00 76. 0
0. 50 48. 6
ably smaller than the volumes of more highly hydrated 1. 00 18. 2
ions such as sodium, calcium, and the like. To determine 25 23 _______________________ _.rlo_.-...._. 1. 03 62.5
Acetic acid.. _. . 50 __________ -_
if the presence of sodium and calcium ions in oil ?eld 24 __________________ _. Amine 220 _____ __ .. l. 00 65. 5

brines might interfere with the action of the ammonium 25 __________________ ._

Cone. HCL.
Ethomeen 8/12..
_.
..
.50
1. Or)
__________ -.
26. 0
and potassium salts, tests 20 to 22 were run. The results 26 __________________ _- Ethomeen 8/12... ___ 1. 00 58. 4
indicate that swelling of shale can be effectively prevented Acetic acid ______ . . . 5O .......... ._

by ammonium sulphate even in the presence of an equal 30

concentration of sodium chloride. A fairly high concen In Table 13 the amines are ldenti?ed principally by
tration of calcium chloride also failed to affect adversely trademarks. Armac C 1s a mixture of amines derived
the swelling inhibiting action of ammonium sulphate. from coconut acids and made water soluble by forming
This is very advantageous since it permits drilling salt the acetate salts. Armac T is the same except the amines
sections with brines substantially saturated with sodium are derived from tallow acids. Intracol CA has been pre
and calcium chloride. This prevents dissolving of the viously de?ned. Intracol 0AM is a methanol solution of
salt by the water used as a drilling ?uid. Test 23 shows Intracol 0A containing about 20 percent methanol.
that Intracol CA has some inhibiting action on the swell Intracol R is the same as Intracol 0 except that it is made
ing of shale. In the presence of a small amount of from coconut oil rather than from oleic acid. Intracol O
Separan, however, the action appears to be substantially 40 is the amine from which the acetate salt, Intracol 0A, is
lost. Tests 25, 26 and 27 demonstrate the highly effective prepared. Aerosol C61 is an ethanolated alkyl guanidine
nature of the preferred combination of additives for pre amine complex. Nalquat G911 is a substituted imida
venting sloughing of shale in clear water drilling. ' zoline which has been quaternized by the addition of a
Tests 29 and 31 show the effectiveness of the preferred hydroxy ethyl and a chlorobutyl group to the secondary
combination of additives on a shale other than the 4:5 nitrogen. Nalcamine G30 is a substituted imidazoline
Pennsylvanian shale used in most of the tests. Tests 32 containing an alkyl and a hydroxy ethyl group. Amine
to 34 show the effects of the additives on still another 220 is a simple alkyl substitute imidazoline. Ethomeen
shale. It will be noted that the degree of swelling in the S/ 12 is an oxyethylated alkyl amine derived from soy
presence of the additives is somewhat greater with this acids. Some of the amines are mixtures. Others are
shale than with the Labette shale. This is to be expected 50 fairly pure compounds. When the term amine is used
since the swelling of the Cherokee shale in the presence hereinafter it is intended to mean either a single amine
of water demonstrates that it is much more susceptible or a mixture of amines. ' ' '
to hydration and swelling than the Pennsylvanian shale. In Table B test 1 shows that in the presence of water
Test 35, when compared to test 26, shows that the presence alone 87 percent of the shale disintegrated to such a
of diesel oil has no adverse e?ects. Test 36 Was conducted 55 degree that it passed through the 30 mesh screen. The 13
at 200 F. The results show that the additives do not percent recovery ?gure is an average of many tests.
lose their effectiveness at elevated temperature. These gave values which varied from a little over 10 to
EXAMPLE 2 as high as 17, depending upon the nature of the particular
shale sample tested. This same variability of shale sam
60 ples should also be taken into consideration in comparing
To determine the abilities of various materials to pre
vent softening of shale by water, 50 gram samples of the effects of the various additives. Tests 2, 3, and 4
Labette shale were placed in pint jars with 350 milliliters show the small effects of ammonium and potassium salts
of water containing the additive to be tested. The jars in decreasing the tendency of the shale to soften. Test 5
were then rolled for 18 hours. The shale placed in the demonstrates the ineffectiveness of the low molecular
65
jars had been ground and screened. All particles passed Weight, organic, nitrogen-containing chemical, urea. Tests
a number 4 sieve and were retained on a number 10 sieve, 6 and 7 show that Separan and diesel oil also have little
U.S. standard series. After rolling, the Water suspension effect by themselves. Tests 8 and 9 demonstrate that
of shale was poured through a number 30 sieve. This combinations of ammonium and potassium salts with
sieve had openings about the same as those in many drill~ 70 Separan are also ineffective for this purpose. ' Tests 10 to
ing ?uid shale shakers. The shale retained on this screen 15, inclusive, not only prove the eifectiveness of two differ
was dried and weighed to determine the percent which ent types of high molecular weight amines in water-soluble
resisted deterioration to such a degree that it would not form, but also provide evidence that the amines or their
pass through the screen. The results of the tests are salts should be used in a concentration of at least about 0.5
reported in Table B. ' 75 pound per barrel if used alone. Later data will show that,

 3,017,351
when used in combination with other ingredients, the con patible with ammonium sulfate. Tests 3 and 7 demon
strate compatibility of the amines with a combination of
centration can be somewhat lower.
Test 16 shows that the amines derived from fallow are ammonium sulfate and Separan. In addition, the com
about as effective as those derived from coconut oil when bination effect of Intracol 0A, the linear polyamine, with
used in the form of the water-soluble acetates. Test 17 Separan is to be noted. This is not observed with the
demonstrates that the presence of methyl alcohol does not cyclic amines. A further combination effect with oil is
substantially affect the effectiveness of Intracol 0A so shown in tests 4 and 10 for the linear amine while test 8
long as the concentration is increased to compensate for shows that no such combination effect is observed in the
the presence of the alcohol. Test 18 shows that, due to case of the cyclic amine. Test 9 is included to show the
the short hydrocarbon radicals in the amines derived 10 compatibility of potassium salts with the other ingredients
from coconut oil and due to the plurality of amine groups in the absence of oil and to show, by comparison to test
in Intracol R, this material is su?iciently water soluble to 10, the combination effect of the oil.
be effective in the absence of a salt-forming acid. EXAMPLE 3
The amines in tests 19, 20 and 21 were also used in the
form of the amine itself rather than its salt. In every The effects of the various additives on the loss of water
case the chemical is a polyamine. This probably explains to formations was determined by measuring the rate of
the effectiveness. Amine 220 tested in tests 22, 23 and ?ow of aqueous solutions of the additives through discs
24 is also a polyamine, being quite similar to Nalcamine of sandstone. The discs were 0.5 inches thick and 2 inches
G-30. In this case, however, the amine de?nitely was in diameter. They were cut from the Nellie Bly sandstone
which lies several feet above the Labette shale series and
not soluble to the extent of 1 pound per barrel of water.
outcrops west of Tulsa, Oklahoma. A pressure difference
The poor results of test 22 indicate the amine was hardly
of 100 pounds was imposed across the discs. The time in
soluble at all. The addition of either acetic acid or hydro
seconds was recorded for successive 100 milliliter portions
chloric acid, however, resulted in the formation of a water
solublesalt which was quite effective. Ethomeen S/ 12 of the various solutions to flow through the discs. The
of tests 25 and 26 was another amine which was only 25 results of tests are reported in Table D.
slightly effective when used alone, but became much
more effective when used as a water-soluble salt. While
the amine itself is water dispersible, the degree of molec Table D
ular dissociation in water apparently was not su?icient in
the absence of an acid to permit effective action by the 30 Additive Water Rate, Seconds for
amine. 100 ml. to Flow
Table C presents data on the compatibility of two
Test
amines with ammonium and potassium salts, with Separan N o. Water-l-Additivc
2610 and with oil. One amine, lntracol CA, has a Ooncen- Water
Type tration Alone
linear polyamine group. The other, Nalcamine G30 has 35 (lb/Dbl.) 1st 2nd 3rd
100 100 100
a cyclic polyamine group.
Separan 26l0 ______ -_ 0.02
1. 00
Table C Separan 2610 ______ ._ 0.02
40 3 {Nalquat Gag-11". 1. 00
"""" " Separan 2610.. __ 0.02

Additive 4 """ " {Aerosol

Separan 0-61
2610 1.00
0.02
Shale
Test No. Recovery 5 """ " {Armac
SeparanT__
2610 1. 00
0.02
Concentra- (Percent)
Type tion (lbs./ 6 """ " {Nalcamine G*30_____
Separan 2010..."..- 1. 00
0.02
bbl.)
7 """ " {Intracol 0A--.
Separan 2610__
___
____
1.00
0.02
Intracol GA. 0.06
Intracol 0A _________ __ 0.5 8 Intracol CA. 0.25
___ 0.5
""" " Intracol OA. 0.50
(NH4)ZS O4 ______ . _ 10.0 Intracol 0A. 1. 00
Intracol 0A _________ _. 0.5
(NH4)2SO4 ...... .. 10.0
Separan 2610. 0.02
Intracol OA____ 0. 5
(NHmS 04. 10.0
Separan 261 0.02
' _______ ._ 1. 8
' The results of test 1 in Table D show the previously
5 ___________________ .. Nalcamiue G-30. _ 0. 5 reported decrease in ?uid loss provided by Separan 2610
6 ___________________ .. Nalcamine 6-30. ___ 0. 5
(NH-D2304 ______ .. 10. 0 alone. Test 8 shows the effects of our preferred amine
7 ___________________ __ Nalcamine G~30_
(NH4)2SO4_--
0. 5
10.0
salt, Intracol 0A, in various concentrations. It will be
Separan 2610. 0.02 apparent from test 8 that, if the amine is used in the
3 ___________________ c. Nalcamine G-30_ 0.5
10.0 absence of Separan, the concentration should be at least
0. 02 about 0.5 pound per barrel of water if a substantial de
1.8
0.5 crease in fluid loss is to be produced. Tests 2 to 7 dem
10. 0 onstrate the effectiveness of combinations of Separan
0. 02
0.5 2610 with several amines. It will be apparent that this
10.0 combination of additives is very effective in decreasing
0.02
1. 8 the loss of water to formations drilled.
EXAMPLE 4

Test 1 in Table C should be compared to test 14 in To determine the effects of the amine and Separan
on the permeability of oil-bearing sands, a test was run
Table B. The difference in results in due in part to varia
tion in the properties of shale samples in the two tests. 70 as described in Example 3 except that the core was ?rst
The difference also illustrates the erratic results which saturated with oil. Then, after the aqueous solution was
forced through the core for a time, oil was caused to
sometimes occur when an amount of amine near the
minimum is used. Test 5 of Table C is identical to test flow back through the core to simulate production of
21 of Table B and is repeated simply for convenience of oil from a well drilled with the aqueous solution. Re
comparison. Tests 2 and 6 show that the amines are com 75 sults of the test are reported in Table E.
 3,017,351
10
Table E and potassium salts to protect shales from the softening
eifects of water. The only requirements seem to be that
Flow Rate the amine be used in a water-soluble form and that it
Liquid Through Core ' ' ' ' contain a hydrocarbon radical long enough to form a
l 100 cc.
Portion
Time,
Seconds
hydrophobic protective ?lm over the shale surfaces. The
?rst requirement can be easily met by forming a water
1 20
soluble salt such as the acetate or chloride if the amine
Diesel Oil I V I g
4 24
itself is not su?iciently water soluble. In this connection,
the term water-soluble amine or amine salt should be
10 interpreted to mean a solubility of at least about 1
Water+0.5 lb. Intracol CA, 0.02 lb. Separan 2610, i it pound of amine or its salt per barrel of water. The
and 10 lb. (NH4)2S04 per barrel of water _______ _. i5 11 second requirement can be met by use of amines having
6 11 hydrocarbon radicals containing at least about 12 carbon
Diesel O1l i3 it atoms.
27 15 For really effective action, most amines should be used
4 27 in concentrations of at least about 1 pound per barrel
of water. Some bene?cial effects are produced, however,
It will be apparent from the data in Table E that, by use of 0.5 pound or less per barrel. In the presence
once a formation is saturated with oil, the amine and of Separan 2610 and oil it Willbe apparent that 0.5 pound
Separan have little tendency to decrease the permeability. per barrel of the linear polyamines such as Intracol 0A
EXAMPLE 5 is more than adequate. Thus, when the combination of
ingredients is used with this particular class of amines, the
Tests were conducted to compare the rate of corrosion amine concentration can be reduced. At least about 0.4
of the water treated for shale drilling, with and without pound per barrel of even the linear polyamines should be
oil, to the corrosion rates of fresh water and brine. The 25 used, however, since the data in Tables B and C show the
results are presented in Table F. The rates of corrosion erratic behavior which may result from use of too little
Were determined by measuring the change in conductance amine.
of a mild steel probe in the ?owing solutions. The concentration of Separan 2610 may be zero if de
Iable F sired since the amines alone provide considerable protec
30 tion to the shale. The concentration of Separan should
normally not exceed about 0.02 pound per barrel of water
Test Corrosion
No. Water Tested Rate, Mils for economic reasons. Most of this additive is lost from
Per Year the drilling ?uid in a single cycle through the well. The
material must, therefore, be added almost continuously.
Fresh water ___________________________________ __ 15. 0 35 This explains the low concentration which is economically
Brine (4% NaOl, 1% (321012, 0.5% MgCli) _____ _. 18. 3
Water+0.5 lb. Intracol 0A, 0.02 lb. Separan 25. 6 feasible. ' To obtain the combination effect with the linear
2610, and 10 lb. (NH4)204 per barrel of water. polyamines, a concentration of at least about 0.005 pound
Same as test 3+0.21 gallon oil per barrel of water. 8. 8
per barrel should be used. This concentration of Separan
will also produce an appreciable reduction in loss of water
The tests in Table F show that a corrosion problem 40
to the formations drilled. ' '
exists when our combination of ammonium or potassium
salt with an amine and Separan is used. The tests also
Oil may also be omitted if desired. In view of the
combination effect with other ingredients, its corrosion in
show, however, that the use of a little oil with the com hibiting ability, and other desirable properties such as
bination decreases the corrosion rate to a value less than its lubricating action, use of about 0.5 gallon of oil per
that caused by fresh water. 45 barrel of water is preferred. At least about 0.1 gallon of
EXAMPLE 6 oil per barrel of water should be added to obtain the com
In view of the successful laboratory tests, the preferred bination effect. The oil may be ordinary crude petroleum
shale drilling ?uid was subjected to shallow well tests in oil available in the ?eld. It is preferred, however, to
which the performance of the solution was compared to 50 use a re?ned petroleum fraction. such as diesel oil.
that of water. The wells were drilled a few feet from Throughout the foregoing description reference has
the edge of a cliff which exposed from the top down been made to clear water, or water substantially free of
solids. Both terms are generally used in the art to de
4 or 5 feet of soil, 5 feet of hard sandstone, and 20 feet
of Labette shale. The formations were not weathered scribe the type of drilling ?uid to which our invention is
since the excavation exposing the formations had been applicable. Both terms, however, may be somewhat mis
made recently. In wells drilled with plain water con leading. We have found that it is solids in the colloidal
particle size range, that is, from about 1 to about 100
taining .02 pound of Separan 2610 per barrel of water,
500 gallons of make-up water were required. In these millimicrons in maximum dimension, which decrease
wells balling of cuttings and sloughing of shale into the drilling rates. Solids which are in true solution, that is,
below the colloidal range, and solids above the colloidal
hole occurred. In addition, on the cliff face adjacent 60 range have relatively little e?fect on drilling rates. It is
to these wells the exposed shale became wet and sloughed. also apparently the absence of colloids in the drilling
In wells drilled with the treated water, no such di?i ?uid which is one of the principal causes for the tend
culties were encountered. Only about 1 extra barrel (42 ency of shales to slough.
gallons) of water was required in drilling these wells. Water may appear clear, but may contain su?icient
No balling or sloughing occurred in the well. There 65 colloids such as starch, sodium carboxymethyl cellulose
was no evidence of water on the cliff face opposite or the like to decrease drilling rates and shale sloughing.
these wells. The treated water contained 10 pounds The term clear water is thus seen to be too broad.
of ammonium sulfate, 0.5 pound of Intracol GA, 0.02 Water may appear to be very muddy and actually may
pound of Separan, and 0.5 gallon of diesel oil per barrel contain many salts in solution and many solids dispersed
of water. It will be apparent from these shallow well 70 as particles above the colloidal range. Such water cer
tests that the advantages appearing in the laboratory tests tainly is not substantially free of solids, but it permits
are realizable in actual well drilling operations. high drilling rates and usually presents problems of shale
When the results reported in the examples are studied, sloughing to which our invention is applicable. For
it becomes apparent that most high molecular weight these reasons, the term water substantially free of col
amines can be used in combination with the ammonium 75 loidally dispersed solids seems best to de?ne the ?eld to
 3,017,351
11 1.2
which our invention is applicable. This term should be polyamine having the nitrogen atoms in a linear non
interpreted to mean water containing less than about 2 cyclic con?guration. e
percent of solids in the colloidal particle size range. 9. The method of claim 8 in which said salt is am
We claim: monium sulfate.
1. A drilling ?uid comprising water substantially free C1 10. The method of drilling a well comprising circulat
of colloidally dispersed solids, containing in each 42~gallon ing in said well in contact with formations containing
barrel of water at least about 3 pounds of a salt selected hydratable shale, water substantially free of colloidally
from the group consisting of water-soluble ammonium dispersed solids, containing in each 42-gallon barrel of
and potassium salts and at least about 0.5 pounds of a water at least about 3 pounds of a salt selected from the
water-soluble form of an amine having a hydrocarbon 10 group consisting of water-soluble ammonium and potas
radical containing at least about 12 carbon atoms. sium salts and at least about 0.5 pound of a water
2. The drilling ?uid of claim 1 in which said amine is soluble form of an amine having a hydrocarbon radical
a polyamine having the nitrogen atoms in a linear non containing at least about 12 carbon atoms.
cyclic con?guration. 11. The method of claim 10 in which said amine is a
3. The drilling ?uid of claim 1 in which said amine is polyamine having the nitrogen atoms in a linear non
in the form of the acetic acid salt of the oleic acid amide cyclic con?guration.
of polyethylene polyamine containing multiple amine References Cited in the ?le of this patent
groups.
4. The drilling ?uid of claim 1 in which said salt is UNITED STATES PATENTS
ammonium sulfate and said amine is a polyamine in 20 1,460,788 Carmen _____________ _.._ July 3, 1923
which the nitrogen atoms are in a linear non-cyclic con 2,315,734 Ralston et al. _________ __ Apr. 6, 1943
?guration. 2,761,843 Brown _.__. __________ .._ Sept. 4, 1956
5. A drilling ?uid comprising water substantially free 2,862,880 Clemens _____________ __ Dec. 2, 1958
of colloidally dispersed solids, containing in each 42-gal 2,873,251 Jones ______________ __ Feb. 10, 1959
lon barrel of water at least about 3 pounds of a salt 25 2,894,907 Newcombe et al. _____ _._ July 14, 1959
selected from the group consisting of water-soluble am 2,960,464 Weiss et al. _________ __ Nov. 15, 1960
monium and potassium salts, at least about 0.4 pound
of a water-soluble form of an amine having a hydrocar FOREIGN PATENTS
bon radical containing at least about 12 carbon atoms, 760,653 Great Britain ________ __ Nov. 7, 1956
at least about 0.005 pound of an acrylamide polymer 799,621 Great Britain _______ __ Aug. 13, 1958
hydrolyte having from about 10 to about 120 amide OTHER REFERENCES
groups for each carboXyl group and having a viscosity
of at least about 4 centipoises for a 0.5 percent by weight McGhee: New Oil Emulsion Speeds West Texas
aqueous solution of said hydrolyte, and at least about Drilling, The Oil and Gas Journal, Aug. 13, 1956, pp.
0.1 gallon of a mineral oil. 35 110-112.
6. The drilling ?uid of claim 5 in which said amine Burdyn et al.: That New Drilling Fluid for Hot
is a polyamine having the nitrogen atoms in a linear non Holes, The Oil and Gas Journal, Sept. 10, 1956, pp.
cyclic con?guration. 104107.
7. The method of drilling a well comprising circulat Mallory: How Low Solids Muds Can Cut Drilling
ing in said well in contact with formations containing 40 Costs, The Petroleum Engineer, April 1957, pp. B21,
hydratable shale, the composition of claim 5. B22, B23 and B24.
8. The method of claim 7 in which said amine is a