U.S. patent number 3,892,275 [Application Number 05/436,290] was granted by the patent office on 1975-07-01 for self-thinning and neutralizing thickened aqueous liquid.
This patent grant is currently assigned to Shell Oil Company. Invention is credited to James H. Lybarger, Ronald F. Scheuerman.
United States Patent |
3,892,275 |
Lybarger , et al. |
July 1, 1975 |
Self-thinning and neutralizing thickened aqueous liquid
Abstract
A thickened aqueous liquid, suitable for suspending packing
particles, comprises an aqueous solution containing an
acid-reactive cellulosic water thickening material, an acidifying
material that causes the solution viscosity to decrease after a
selected time-temperature exposure, and a relatively slowly
reactive material that causes the solution pH to increase to a
selected value after a longer time.
Inventors: |
Lybarger; James H. (Metairie,
LA), Scheuerman; Ronald F. (Bellaire, TX) |
Assignee: |
Shell Oil Company (Houston,
TX)
|
Family
ID: |
23731870 |
Appl.
No.: |
05/436,290 |
Filed: |
January 24, 1974 |
Current U.S.
Class: |
166/250.01;
166/278; 166/300; 166/307 |
Current CPC
Class: |
E21B
43/045 (20130101); E21B 47/00 (20130101); C09K
8/90 (20130101) |
Current International
Class: |
E21B
47/00 (20060101); E21B 43/04 (20060101); E21B
43/02 (20060101); C09K 8/90 (20060101); C09K
8/60 (20060101); E21B 043/04 (); E21B 043/27 () |
Field of
Search: |
;166/250,278,294,307,270,300,35R |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Novosad; Stephen J.
Assistant Examiner: Suckfield; George
Claims
What is claimed is:
1. A well treating process which comprises:
determining the approximate time and temperature to which a fluid
will be subjected when the fluid has a selected viscosity and is
pumped at a selected rate to a zone to be treated within the
well;
compounding an aqueous liquid that contains (a) enough dissolved
acid-reactive cellulosic water thickener to provide the selected
viscosity, (b) an amount and composition of substantially
homogeneously distributed acidifying material sufficient to cause a
decrease in the solution viscosity at a selected time after the
solution reaches said zone when pumped at said rate; and (c) an
amount of substantially homogeneously distributed relatively slowly
reactive pH-increasing material sufficient to raise the pH of the
solution to a selected substantially neutral value within a
selected additional time; and
pumping the compounded aqueous liquid into the well at a rate
substantially equalling the selected rate.
2. The process of claim 1 in which a sand or gravel pack is formed
by suspending packing grains in the compounded aqueous liquid
before it is pumped into the well.
3. The process of claim 2 in which said acidifying material and pH
increasing material are dissolved in said aqueous solution of
cellulosic material.
4. The process of claim 2 in which the injection of the aqueous
liquid containing the suspended grains is preceded by an injection
of a slug of acid ahead of a slug of said compounded aqueous liquid
that is free of suspended grains.
5. The process of claim 1 in which said acidifying and
pH-increasing materials are, respectively, hydrochloric acid and a
mixture of acetamide and urea.
Description
BACKGROUND OF THE INVENTION
The present invention relates to a thickened aqueous liquid and its
use in well treating processes, such as sand or gravel packing,
fracturing, fluid-diverting, selective-plugging, fluid-displacing,
or the like, processes.
Prior well treating processes have used thickened aqueous liquids,
and some of them have used cellulosic material water thickeners and
acidic material viscosity breakers. Prior well treating processes
are described in U.S. patents such as: U.S. Pat. No. 3,778,472,
describing cellulose ether-thickened reservoir acidizing solutions
that are self-thinning; U.S. Pat. No. 3,024,195, describing
fracturing fluids that are thickened with carboxymethylcellulose
and thinned by a dissolved perborate; U.S. Pat. No. 3,417,820,
describing aqueous solutions of alkaline earth metal salts that are
thickened with hydroxyethylcellulose and thinned with an oxidative
or enzymatic breaker; U.S. Pat. No. 3,696,035, describing aqueous
alcoholic solutions that are thickened with cellulose derivatives
and thinned with a periodate or other oxidizing or reducing
material, etc. The previously proposed acid-thinned aqueous
solutions tend to become and/or remain relatively strongly acidic
and thus corrosive. The thinning action of an oxidizying or
reducing reactant in an aqueous solution containing a cellulosic
thickening material tends to be unpredictably accelerated when the
solution entrains in atmospheric oxygen in amounts that are apt to
be unavoidable in the handling of fluids at a well site.
SUMMARY OF THE INVENTION
This invention provides a thickened aqueous liquid containing (a)
enough dissolved acid-reactive cellulosic water thickener to
provide a selected viscosity, (b) an amount and composition of
substantially homogeneously distributed acidifying material
sufficient to cause a decrease in the viscosity of the solution
after a selected time-temperature exposure, and (c) an amount and
composition of substantially homogeneously distributed relatively
slowly-reactive pH-increasing material sufficient to raise the pH
of the solution to a selected substantially neutral value after an
additional time.
The invention also provides a well treating process comprising:
determining the approximate time and temperature to which a fluid
having a selected viscosity is subjected while being pumped, at a
selected rate, into a zone to be treated within a well; compounding
an aqueous liquid that contains (a) enough dissolved acid-reactive
cellulosic water thickener to provide the selected viscosity (b) an
amount and composition of substantially homogeneously distributed
acidifying material sufficient to cause a decrease in the solution
viscosity within a selected time after the solution, when pumped at
the selected rate, has reached a selected depth within the well,
and (c) an amount and composition of substantially homogeneously
distributed relatively slowly reactive pH-increasing material
sufficient to raise the pH of the solution to a selected
substantially neutral value within a selected additional time; and,
pumping the compounded aqueous liquid into the well at
substantially the selected rate.
The present composition and process are useful in various
operations, such as suspending and/or transporting substantially
any dissolved or dispersed materials that are relatively inert with
respect to the viscosity-reducing and acid-neutralizing
reactions.
DESCRIPTION OF THE DRAWING
FIGS. 1 and 2 show portions of a well and adjoining subterranean
regions suitable for treatment in accordance with the present
invention.
FIG. 3 shows a plot of the viscosity with time of various
hydroxyethylcellulose-thickened aqueous solutions.
DESCRIPTION OF THE INVENTION
The invention is, at least in part, premised on a discovery that:
by using an acid-sensitive cellulosic water thickener and a slowly
reactive pH-increasing material, the occurrence of a self-thinning
action within the thickened aqueous liquid can be relatively
accurately timed with respect to rather widely varying
time-temperature exposures, and the thinned solution can be caused
to become a substantially neutral liquid that is non-corrosive to
equipment such as that contained in a well.
Generally suitable acid-reactive cellulosic water thickeners
include acid-sensitive cellulose ethers such as the hydroxyalkyl,
carboxyalkyl, and lower alkyl, cellulose ethers, typified by
hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, or
the like, which are substantially completely aqueous-liquid-soluble
cellulose ethers that form substantially completely
aqueous-liquid-soluble hydrolysis products when hydrolyzed in an
acidic aqueous liquid. The hydroxyethylcellulose "Natrosol,"
available from Hercules Powder Company, J-164 from Dowell, or WG-8
from Halliburton, are particularly suitable.
Generally suitable acidifying materials include acids or
acidyielding materials that are adapted to be dissolved or
substantially homogeneously distributed in an aqueous solution of
the cellulosic thickening material. The acidic materials preferably
reduce the pH of the solution to at least as low as about 4.0.
Suitable materials include mineral acids such as hydrochloric acid,
organic acids such as formic acid, hydrolyzable esters of organic
acids such as methyl formate, hydrolyzable organic halides such as
tertiarybutylchloride, etc. For relatively low temperature or
short-time temperature exposures, acids such as hydrochloric acid
or formic acid are particularly suitable. For relatively higher
temperatures or longer time-temperature exposures, esters such as
methyl formate are particularly suitable.
Generally suitable pH-increasing materials include compounds or
mixtures of compounds that react with water, or react in the
presence of water, to form water-soluble reaction products that
increase the pH of an acidic aqueous solution by neutralizing or
spending the acidity of the solution. Such materials include:
amides of carbamic acid, urea, the homologues of urea, the salts of
cyanic acid, organic acid amides such as formamide,
dimethylformamide, acetamide, etc. Urea and the lower organic
amides, such as formamide and acetamide, or the like, are
particularly suitable. In various situations, the present thickened
aqueous liquids can comprise either a solution or a substantially
homogeneous emulsion or dispersion of the acidifying and
pH-increasing materials and the aqueous liquid solution of
cellulosic material, as long as the components are substantially
homogeneously distributed in that solution so that each portion of
the solution contains a substantially equivalent proportion of each
reactant.
In general, the concentration of the cellulosic material thickener
in the aqueous solution can be varied substantially as desired to
obtain the selected degree of viscosity. The proportion of
dissolved cellulose material can range from about 0.1 to 4 percent
by weight of the solution to provide viscosities which (at normal
surface temperatures of about 80.degree.F) range from about 100 to
51,000 centipoise.
The amount and composition of the acidifying material is adjusted
to be sufficient to cause a substantially complete breaking of the
solution viscosity (preferably to a viscosity near that of water)
after a selected time-temperature exposure of the solution. As
known to those skilled in the art, increases in the amount of acid
that is initially dissolved in the solution, or increases in the
rate at which the acid is formed within the solution, or increases
in the strength of the acid (e.g., using a strong acid such as
hydrochloric acid, or a relatively weak acid such as formic acid,
or a mixture of strong and weak acids rather than using only a weak
acid) decrease the amount of time-temperature exposure that is
needed to induce the viscosity-breaking. The present thickened
aqueous liquids can be formulated to break after times such as from
about 4-24 hours after being pumped into a subterranean zone having
a temperature of from about 100.degree.-300.degree.F.
The amount and composition of the pH-increasing material is
adjusted to ultimately raise the pH of the solution to a selected
substantially neutral value. As known to those skilled in the art,
the rate of the pH-increasing is affected by the composition and
concentration of the pH-increasing reactant. The rate should be
adjusted to allow sufficient acidity to remain (or be developed) in
the aqueous solution of cellulosic material to cause the desired
viscosity-breaking and subsequently raise the pH to the selected
value, within a selected additional time at the temperature of the
zone being treated. Where desired, the amount of the pH-increasing
material can be sufficient to ultimately provide a solution pH of 7
(a neutral solution) or more (an alkaline solution). Since the
acid-induced hydrolysis of the cellulosic material does not "spend"
or neutralize the acid, where a complete neutralization is desired
the proportions of acidizing and pH-increasing materials should
include at least a stoichiometric equivalent of the pH-increasing
reactant. In addition, the pH-increasing reactant can be arranged
to form a buffered solution that attains and maintains a selected
pH, such as one from about 4 to 6. Such a pH-buffering can
advantageously be obtained by the combination of reactants, such as
urea and acetamide that provide a mixture of a weak acid and a
soluble salt of a weak acid (i.e., a buffer system).
The thickened aqueous liquids of the present invention can also
contain substantially any of the conventionally used additives for
packing or fracturing fluids. Such additives commonly include
density-increasing salts, corrosion inhititors, wetting agents,
etc. Such additives are suitable as long as they are compatible
with the cellulosic thickener, acidic breaker and pH-increasing
reactants. Suitable weight-imparting salts include the monovalent
metal or ammonium chlorides, such as 1-5% wt. solutions of ammonium
or potassium chloride. The use of ammonium chloride is particularly
preferred where the thickened liquid may be preceded or followed by
a mud acid.
FIGS. 1 and 2 show a particularly advantageous utilization of the
present invention. A well borehole 1 is equipped with a string of
casing 2 that is surrounded by cement 3 and penetrated by
perforations 4 within a subterranean reservoir 6. The casing is
equipped with an internal pipe string 7 associated with a packing
device 8, a fluid crossover means 9, a screening or filtering
device 11, and a check valve means 12. The borehole equipment can
comprise devices that are commercially available. Such equipment is
preferably arranged for an injection of fluid into a subterranean
reservoir as shown by the arrows.
In accordance with the invention, a sand or gravel pack 13 is
emplaced within the perforations, the associated perforation,
tunnels (and/or voids) in the adjacent reservoir, and the annular
space between the screen 11 and the casing 2 (as shown in FIG. 2).
The packing granules are emplaced by suspending them in a
self-thinning and neutralizing solution of the present invention
and pumping the suspension into the well (preferably as shown by
the arrows in FIG. 1.) until the grains are screened out against
the face of the reservoir. As known to those skilled in the art,
such a "sand-out" is identifiable by a significant increase in the
fluid injection pressure, and usually occurs when much of the space
between the pipe string 7 and the casing 2 is filled with the
suspension.
After the selected time-temperature exposure, the viscosity of the
present self-thinning fluid breaks and allows the suspended grains
to settle. Subsequently, that fluid, of which a significant portion
may remain in the space between the tubing and casing, becomes a
self-neutralized static liquid 14 (see FIG. 2). Such a
self-neutralization is particularly advantageous. When fluid is
produced from the reservoir, it tends to flow directly through the
screen 11 into the pipe string 7, (as shown by the arrows in FIG.
2), without displacing the substantially static fluid in the
annulus between the pipe string and the casing. If such a static
fluid contains unneutralized acid, or contains an unreacted excess
of oxidizing agent, it can be relatively corrosive and can damage
the casing and cause a loss of the well.
The injection of a suspension of gravel packing grains is often
preceded by injecting a slug of acid to increase the reservoir
permeability. In such a procedure, a slug of viscous brine can be
positioned between the acid and the suspension in order to keep the
grainsuspending slurry from contacting the acid. It is desirable to
ensure that all of the perforation tunnels and/or voids within the
reservoir are completely and tightly packed. Therefore, reltively
high pressures and large volumes of fluid are often used to force a
significant amount of fluid through the packing grains that are
screened out against the face of the reservoir. This displaces a
significant portion of the grain suspending liquid into the
reservoir in a zone surrounding the well from which fluids will be
produced when the well (if it is a production well) is returned to
production.
In a particularly preferred embodiment of the present invention,
the liquid in which the packed grains are suspended, (i.e., the
present self-thinning and neutralizing aqueous liquid) is preceded
by both a pretreatment slug of acid comprising a self-neutralizing
aqueous liquid solution of an acid and pH-increasing material, and
a buffer slug of substantially inert salt, such as ammonium
chloride, sodium chloride, or the like. In this embodiment it is
thus ensured that (when the well being treated is an oil well)
substantially all of the aqueous fluids which are mingled with the
reservoir oil have a selected substantially neutral pH. This avoids
an "acid upset," due to the formation of an emulsion. Such
emulsions are formed when various reservoir crudes, such as those
encountered near the Gulf of Mexico, are mingled with relatively
strongly acidic aqueous liquids.
FIG. 3 shows the effects of time at various temperatures on (1) an
aqueous solution of 80 pounds of hydroxyethylcellulose (HEC) per
100 gallons of water, 10 grams per liter potassium chloride, 2
moles per liter of methyl formate, and 0.1 pound per barrel of
sodium hydroxide, and (2) an otherwise similar (but unacidified)
HEC solution that contained no methyl formate. In an aqueous
solution, methyl formate hydrolyzes to formic acid and methyl
alcohol. And, the hydrolysis reaction is acid-catalyzed. As shown
by FIG. 3., the solutions containing methyl formate and HEC are
hydrolyzed at increasingly rapid rates and undergo increasingly
rapid decreases in viscosity.
At 180.degree.F, the viscosity of the non-acidified 80-pound per
1,000 gallon HEC solution (about 8% by weight HEC) decreased
slowly; by only about 50% in about 36 hours. In contrast, when a
similar solution contained 2 moles of methyl formate, its viscosity
was reduced by 99% in about 9 hours, and became as low as about 1
centipoise in about 24 hours. At lower temperatures, longer times
are required to obtain the viscositybreak, due to the decreased
rate of hydrolysis of both the methyl formate and the
hydroxyethylcellulose. As indicated by the pH curves for the methyl
formate-containing solutions at 140.degree. and 160.degree.F, a
significant acceleration in viscosity reduction does not occur
until the solution pH becomes less than about 2.5. Such tests, in
the light of field experience, have indicated the suitability of
acidifying materials including dilute HCl, formic acid, acetic-acid
and methyl formate, for inducing the viscosity breaking for
treatments conducted at temperatures of from about 110.degree. to
200.degree.F. Field experience has shown that the relatively rapid
viscosity breaking reactions, such as those of HCl, at temperatures
above about 130.degree.F, cause substantially no problem in
treating reservoirs at significantly higher temperatures. The
available variations in pumping times, pre-injections of relatively
cool fluid, etc., were found to be sufficient for ensuring that the
slurries were emplaced before their viscosities were reduced.
The following exemplifies a process of gravel packing an oil
production well, where the reservoir being treated is about 7,500
feet deep, is about 20 feet thick, and has a temperature of about
150.degree.F. The well is preferably equipped as shown in FIG. 1.
The first solution injected is a pretreatment slug of about 1,000
gallons of an aqueous solution of 7.5% hydrochloric acid and 1.5%
hydrofluoric acid, 1.65 moles per liter of urea and 1.5 moles per
liter of acetamide. The acid preflush is followed by a buffer slug
of about 2 barrels of 3% of ammonium chloride in water. The buffer
slug is followed by about 3 barrels of a self-thinning and
neutralizing brine containing about 8% by weight
hydroxyethylcellulose solution, 1 mole per miter of hydrochloric
acid, 1 mole per liter of urea, and 1.5 mole per liter of
acetamide. The self-thinning and neutralizing brine solution is
followed by about 10-12 barrels of a pack slurry comprising the
same self-neutralizing and thinning solution in which there is
suspended about 15 pounds per gallon of 20-40 mesh gravel pack
sand. The pack slurry is displaced ahead of an amount of aqueous
brine sufficient to move its rear edge through the packer 8 and
into the space between the pipe string 7 and the casing 2. The
so-treated well is allowed to stand for about 24 hours and then
returned to production.
* * * * *