U.S. patent application number 09/307545 was filed with the patent office on 2001-12-06 for well kill additive, well kill treatment fluid made therefrom, and method of killing a well.
Invention is credited to BURTS, JR., BOYCE D..
Application Number | 20010049403 09/307545 |
Document ID | / |
Family ID | 25505558 |
Filed Date | 2001-12-06 |
United States Patent
Application |
20010049403 |
Kind Code |
A1 |
BURTS, JR., BOYCE D. |
December 6, 2001 |
WELL KILL ADDITIVE, WELL KILL TREATMENT FLUID MADE THEREFROM, AND
METHOD OF KILLING A WELL
Abstract
For well kill treatment to prevent the intrusion of formation
fluids into the wellbore while the well is open, a well kill
additive including a dry mixture of water soluble crosslinkable
polymer, a crosslinking agent, and a reinforcing material of fibers
and/or comminuted plant materials. The method of forming a well
kill fluid includes contacting the additive with water or an
aqueous solution, with a method of conforming the formation further
including the step of injecting the fluid into the wellbore.
Inventors: |
BURTS, JR., BOYCE D.;
(MARICE, LA) |
Correspondence
Address: |
GILBRETH & ASSOCIATES, P.C.
P O BOX 61305
HOUSTON
TX
77208-1305
US
|
Family ID: |
25505558 |
Appl. No.: |
09/307545 |
Filed: |
May 7, 1999 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
09307545 |
May 7, 1999 |
|
|
|
08962213 |
Oct 31, 1997 |
|
|
|
6016869 |
|
|
|
|
Current U.S.
Class: |
523/130 ;
523/131; 523/132 |
Current CPC
Class: |
C09K 8/44 20130101; Y10S
507/904 20130101; C09K 8/512 20130101; Y10S 507/903 20130101 |
Class at
Publication: |
523/130 ;
523/131; 523/132 |
International
Class: |
C09K 007/00; C09K
017/00 |
Claims
I claim:
1. A well kill additive comprising a dry mixture of a water soluble
crosslinkable polymer, a crosslinking agent, and a reinforcing
material selected from among fibers and comminuted plant
materials.
2. The additive of claim 1 wherein the polymer is an a
carboxylate-containing polymer and the crosslinking agent is a
chromic carboxylate complex.
3. The additive of claim 2 wherein the reinforcing material
comprises hydrophilic and hydrophobic fibers.
4. The additive of claim 3 wherein the hydrophobic fibers comprise
at least one selected from the group of hydrophobic fibers
consisting essentially of nylon, rayon, and hydrocarbon fibers, and
wherein the hydrophilic fibers comprise at least one selected from
the group of hydrophilic fibers consisting essentially of glass,
cellulose, carbon, silicon, graphite, calcined petroleum coke, and
cotton fibers.
5. The additive of claim 2 wherein the reinforcing material
comprises comminuted plant material.
6. The additive of claim 5 wherein the reinforcing material
comprises at least one comminuted material selected from the group
of comminuted plant materials consisting essentially of nut and
seed shells or hulls of almond, brazil, cocoa bean, coconut,
cotton, flax, grass, linseed, maize, millet, oat, peach, peanut,
rice, rye, soybean, sunflower, walnut, and wheat; rice tips; rice
straw; rice bran; crude pectate pulp; peat moss fibers; flax;
cotton; cotton linters; wool; sugar cane; paper; bagasse; bamboo;
corn stalks; sawdust; wood; bark; straw; cork; dehydrated vegetable
matter; whole ground corn cobs; corn cob light density pith core;
corn cob ground woody ring portion; corn cob chaff portion; cotton
seed stems; flax stems; wheat stems; sunflower seed stems; soybean
stems; maize stems; rye grass stems; millet stems; and mixtures
thereof.
7. The additive of claim 2 wherein the polymer is a partially
hydrolyzed polyacrylamide.
8. The additive of claim 7 wherein the reinforcing material is a
comminuted material selected from among comminuted materials
derived from peanuts, wood, paper any portion of rice seed or
plant, any portion of corn cobs, and mixtures thereof.
9. The additive of claim 8 wherein the additive further includes
cellophane, and wherein the reinforcing material is a comminuted
material selected from among mixtures of comminuted rice fraction
and peanut hulls; mixtures of comminuted rice fraction, and wood
fiber or almond hulls; mixtures of comminuted rice fraction and
corn cob fraction; and mixtures of comminuted rice fraction and
corn cob fraction and at least one of wood fiber, nut shells, and
paper.
10. The additive of claim 9 wherein the reinforcing material
comprises comminuted mixture of rice fraction, corn cob pith and
chaff, cedar fiber, nut shells, and paper.
11. A method of forming a well kill fluid comprising: (a) providing
a well kill additive comprising a dry mixture of water soluble
crosslinkable polymer, a crosslinking agent, and a reinforcing
material selected from among fibers and comminuted plant materials;
and (b) contacting the well kill additive with water or an aqueous
solution to form the well kill fluid.
12. The method of claim 11 wherein the polymer is a partially
hydrolyzed polyacrylamide, the crosslinking agent is a chromic
carboxylate complex, wherein the additive further includes
cellophane, and wherein the reinforcing material is a comminuted
material selected from among mixtures of comminuted rice fraction
and peanut hulls; mixtures of comminuted rice fraction, and wood
fiber or almond hulls; mixtures of comminuted rice fraction and
corn cob fraction; and mixtures of comminuted rice fraction and
corn cob fraction and at least one of wood fiber, nut shells, and
paper.
13. The additive of claim 12 wherein the reinforcing material
comprises comminuted mixture of rice fraction, corn cob pith and
chaff, cedar fiber, nut shells, and paper.
14. A method of killing a well to substantially reduce volumetric
flow of a formation fluid across a wellbore face into a wellbore
penetrating a formation having a formation matrix and containing
said formation fluid below an earthen surface, comprising: (a)
providing a well kill additive comprising a dry mixture of water
soluble crosslinkable polymer, a crosslinking agent, and a
reinforcing material selected from among fibers and comminuted
plant materials; (b) contacting said additive with water to for a
well kill fluid; (c) placing said well kill fluid in said wellbore
at said wellbore face, wherein said fluid which is placed at said
wellbore face does not significantly penetrate the formation
matrix; (d) forming a nonflowing fluid from said well kill fluid in
said wellbore at said wellbore face to substantially reduce said
volumetric flow of said formation fluid across said wellbore face
into said wellbore, thereby killing said well; and (e) removing
substantially all of said nonflowing fluid from said wellbore face
to substantially restore the volumetric flow of said formation
fluid into said wellbore.
15. The method of claim 14 wherein the polymer is an a
carboxylate-containing polymer and the crosslinking agent is a
chromic carboxylate complex.
16. The method of claim 15 wherein the reinforcing material
comprises hydrophilic and hydrophobic fibers.
17. The method of claim 16 wherein the hydrophobic fibers comprise
at least one selected from the group of hydrophobic fibers
consisting essentially of nylon, rayon, and hydrocarbon fibers, and
wherein the hydrophilic fibers comprise at least one selected from
the group of hydrophilic fibers consisting essentially of glass,
cellulose, carbon, silicon, graphite, calcined petroleum coke, and
cotton fibers.
18. The method of claim 15 wherein the reinforcing material
comprises comminuted plant material.
19. The method of claim 18 wherein the reinforcing material
comprises at least one comminuted material selected from the group
of comminuted plant materials consisting essentially of nut and
seed shells or hulls of almond, brazil, cocoa bean, coconut,
cotton, flax, grass, linseed, maize, millet, oat, peach, peanut,
rice, rye, soybean, sunflower, walnut, and wheat; rice tips; rice
straw; rice bran; crude pectate pulp; peat moss fibers; flax;
cotton; cotton linters; wool; sugar cane; paper; bagasse; bamboo;
corn stalks; sawdust; wood; bark; straw; cork; dehydrated vegetable
matter; whole ground corn cobs; corn cob light density pith core;
corn cob ground woody ring portion; corn cob chaff portion; cotton
seed stems; flax stems; wheat stems; sunflower seed stems; soybean
stems; maize stems; rye grass stems; millet stems; and mixtures
thereof.
20. The method of claim 15 wherein the polymer is a partially
hydrolyzed polyacrylamide.
21. The method of claim 20 wherein the reinforcing material is a
comminuted material selected from among comminuted materials
derived from peanuts, wood, paper any portion of rice seed or
plant, any portion of corn cobs, and mixtures thereof.
22. The method of claim 21 wherein the additive further includes
cellophane, and wherein the reinforcing material is a comminuted
material selected from among mixtures of comminuted rice fraction
and peanut hulls; mixtures of comminuted rice fraction, and wood
fiber or almond hulls; mixtures of comminuted rice fraction and
corn cob fraction; and mixtures of comminuted rice fraction and
corn cob fraction and at least one of wood fiber, nut shells, and
paper.
23. The method of claim 22 wherein the reinforcing material
comprises comminuted mixture of rice fraction, corn cob pith and
chaff, cedar fiber, nut shells, and paper.
24. A method for reducing volumetric flow of a formation fluid
across a wellbore face into a wellbore penetrating a formation
having a formation matrix and containing said formation fluid below
an earthen surface, comprising:: (a) providing a well kill fluid
comprising an aqueous solution of water soluble crosslinkable
polymer, a crosslinking agent, and a reinforcing material selected
from among fibers and comminuted plant materials; (b) placing said
well kill fluid in said wellbore at said wellbore face, wherein
said fluid which is placed at said wellbore face does not
significantly penetrate the formation matrix; (c) forming a
nonflowing fluid from said well kill fluid in said wellbore at said
wellbore face to substantially reduce said volumetric flow of said
formation fluid across said wellbore face into said wellbore,
thereby killing said well; and (d) removing substantially all of
said nonflowing fluid from said wellbore face to substantially
restore the volumetric flow of said formation fluid into said
wellbore.
25. The method of claim 24 wherein the polymer is an a
carboxylate-containing polymer and the crosslinking agent is a
chromic carboxylate complex.
26. The method of claim 25 wherein the reinforcing material
comprises hydrophilic and hydrophobic fibers.
27. The method of claim 26 wherein the hydrophobic fibers comprise
at least one selected from the group of hydrophobic fibers
consisting essentially of nylon, rayon, and hydrocarbon fibers, and
wherein the hydrophilic fibers comprise at least one selected from
the group of hydrophilic fibers consisting essentially of glass,
cellulose, carbon, silicon, graphite, calcined petroleum coke, and
cotton fibers.
28. The method of claim 25 wherein the reinforcing material
comprises comminuted plant material.
29. The method of claim 28 wherein the reinforcing material
comprises at least one comminuted material selected from the group
of comminuted plant materials consisting essentially of nut and
seed shells or hulls of almond, brazil, cocoa bean, coconut,
cotton, flax, grass, linseed, maize, millet, oat, peach, peanut,
rice, rye, soybean, sunflower, walnut, and wheat; rice tips; rice
straw; rice bran; crude pectate pulp; peat moss fibers; flax;
cotton; cotton linters; wool; sugar cane; paper; bagasse; bamboo;
corn stalks; sawdust; wood; bark; straw; cork; dehydrated vegetable
matter; whole ground corn cobs; corn cob light density pith core;
corn cob ground woody ring portion; corn cob chaff portion; cotton
seed stems; flax stems; wheat stems; sunflower seed stems; soybean
stems; maize stems; rye grass stems; millet stems; and mixtures
thereof.
30. The method of claim 25 wherein the polymer is a partially
hydrolyzed polyacrylamide.
31. The method of claim 30 wherein the reinforcing material is a
comminuted material selected from among comminuted materials
derived from peanuts, wood, paper any portion of rice seed or
plant, any portion of corn cobs, and mixtures thereof.
32. The method of claim 31 wherein the additive further includes
cellophane, and wherein the reinforcing material is a comminuted
material selected from among mixtures of comminuted rice fraction
and peanut hulls; mixtures of comminuted rice fraction, and wood
fiber or almond hulls; mixtures of comminuted rice fraction and
corn cob fraction; and mixtures of comminuted rice fraction and
corn cob fraction and at least one of wood fiber, nut shells, and
paper.
33. The method of claim 32 wherein the reinforcing material
comprises comminuted mixture of rice fraction, corn cob pith and
chaff, cedar fiber, nut shells, and paper.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to well kill additives, to
well kill treatment fluids made therefrom, to methods of killing a
well. In another aspect, the present invention relates to well kill
additives comprising polymer and fibers or comminuted plant
materials, to well kill treatment fluids made therefrom, to methods
of killing a well.
[0003] 2. Description of the Related Art
[0004] Kill fluids are commonly placed in a wellbore during oil
field wellbore operations, including drilling, wellbore
completions, and workovers, to kill the well, i.e., prevent the
intrusion of formation fluids into the wellbore while the well is
open. The kill fluid is often maintained in the wellbore for the
entire duration of the operation.
[0005] Conventional kill fluids known in the art are typically
aqueous liquids, which contain a weighting agent, such as inert
inorganic solids in solution or suspension, to increase the density
of the fluid. The weighted kill fluid applies a hydrostatic
pressure against the formation fluid, which is greater than the
pressure exerted by the formation fluid attempting to intrude into
the wellbore. This overbalanced hydrostatic pressure prevents the
intrusion of formation fluids into the wellbore during performance
of the given oil field wellbore operation which is necessary from
an operational standpoint to prevent interference from formation
fluids and which is also necessary from a safety standpoint.
Maintenance of a sufficient hydrostatic pressure in the wellbore
reduces the potential of a well kick or blow out.
[0006] Thickeners are often included in weighted kill fluids known
in the art for leakoff inhibition. See, for example, Hudson et al,
SPE Paper No. 10652, which discloses a weighted brine containing a
fluid loss control agent, or U.S. Pat. No. 4,391,925 to Mintz et
al, which discloses a multi-phase kill fluid comprising a number of
constituents including a hydrocarbon, a surfactant, a clay and an
organic polymer. Advantageous kill fluids are those which prevent
formation fluid intrusion into the wellbore while preventing
appreciable wellbore fluid leakoff into the formation. Fluid
leakoff can undesirably result in formation damage, i.e.,
permeability reduction, which is manifested in reduced hydrocarbon
recovery from the formation or reduced injectivity into the
formation.
[0007] Under downhole conditions where the wellbore is in direct
communication with voids, it can be extremely difficult to prevent
fluid leakoff. Conventional kill fluids generally do not exhibit
sufficient flow resistance to prevent them from escaping the
wellbore into the formation matrix via the high permeability voids.
Such leakoff can ultimately result in loss of the hydrostatic
pressure overbalance which enables formation fluids to intrude into
the wellbore, negating the primary function of the kill treatment.
Although it is possible to maintain the hydrostatic pressure
overbalance in the face of severe fluid leakoff by replenishing the
lost kill fluid, this practice can be cost prohibitive.
[0008] U.S. Pat. No. 4,995,461, issued Feb. 26, 1991 to Sydansk
noted that the utility of kill fluids was limited, particularly in
the presence of voids in direct communication with the wellbore,
and further noted a need existed for a kill treatment having
utility in hydrocarbon recovery operations over a broad range of
operating conditions, and particularly having utility when kill
fluids are ineffective. Sydansk even further noted a need existed
for a kill treatment, which is effective when severe voids in
direct communication with the wellbore are present. Sydansk still
further noted that a kill treatment was needed which prevents or
minimizes the intrusion of formation fluids into the wellbore and
prevents or minimizes the significant leakoff of wellbore fluid
from the wellbore in the presence of such voids.
[0009] In an effort to overcome deficiencies noted by him in the
prior art, Sydansk proposed in both U.S. Pat. Nos. 4,947,935, and
4,995,461, the use of a water soluble carboxylate crosslinking
polymer along with a chromic carboxylate complex crosslinking agent
for well kill treatment. Sydansk further teaches that the
performance requirements of conformance improvement treatment
polymers are different from those of kill treatment polymers. Thus,
while U.S. Pat. No. 5,377,760, issued Jan. 3, 1995 to Merrill
discloses addition of fibers to an aqueous solution of partially
hydrolyzed polyacrylamide polymer, with subsequent injection into
the subterranean to improve conformance, Sydansk teaches that such
would not necessarily work for kill treatment.
[0010] Additionally, Merrill's conformance treatment method of
mixing the fibers with the polymer solution followed by injection,
requires a multiplicity of storage and mixing tanks, and a metering
system which must be operated during the operation of the well.
Specifically, a first tank will store a water and polymer solution,
a second tank will store a water and cross-linking solution, and a
third tank will be used to mix fibers with polymer solution from
the first tank to create a polymer/fiber slurry. This polymer/fiber
slurry is then metered from the third tank and combined with
crosslinking solution metered from the second tank to the well
bore.
[0011] Thus, in spite of the advancements in the prior art, there
still need for further innovation in well kill additives.
[0012] There is need for further innovation for well kill additives
utilizing a water soluble polymer.
[0013] There is another need for a well kill additive which would
allow for simplification of the mixing equipment.
[0014] These and other needs in the art will become apparent to
those of skill in the art upon review of this specification,
including its drawings and claims.
SUMMARY OF THE INVENTION
[0015] It is an object of the present invention to provide for
further innovation in well kill additives.
[0016] It is an another object of the present invention to provide
for further innovation for well kill additives utilizing a water
soluble polymer.
[0017] It is even another object of the present invention to
provide for a well kill additive which would allow for
simplification of the mixing equipment.
[0018] These and other objects of the present invention will become
apparent to those of skill in the art upon review of this
specification, including its drawings and claims.
[0019] According to one embodiment of the present invention there
is provided a well kill additive comprising a dry mixture of water
soluble crosslinkable polymer, a crosslinking agent, and a
reinforcing material selected from among fibers and comminuted
plant materials. In preferred embodiments, the polymer is an a
carboxylate-containing polymer and the crosslinking agent is a
chromic carboxylate complex. In other preferred embodiments, the
reinforcing material may comprise hydrophobic fibers selected from
among nylon, rayon, and hydrocarbon fibers, and/or hydrophilic
fibers selected from among glass, cellulose, carbon, silicon,
graphite, calcined petroleum coke, and cotton fibers. The
comminuted plant material is selected from the group of comminuted
plant materials of nut and seed shells or hulls of almond, brazil,
cocoa bean, coconut, cotton, flax, grass, linseed, maize, millet,
oat, peach, peanut, rice, rye, soybean, sunflower, walnut, and
wheat; rice tips; rice straw; rice bran; crude pectate pulp; peat
moss fibers; flax; cotton; cotton linters; wool; sugar cane; paper;
bagasse; bamboo; corn stalks; sawdust; wood; bark; straw; cork;
dehydrated vegetable matter; whole ground corn cobs; corn cob light
density pith core; corn cob ground woody ring portion; corn cob
chaff portion; cotton seed stems; flax stems; wheat stems;
sunflower seed stems; soybean stems; maize stems; rye grass stems;
millet stems; and mixtures thereof.
[0020] According to another embodiment of the present invention,
there is provided a method of forming a well kill fluid. The method
generally includes taking the above well kill additive and
contacting it with water or other aqueous solution.
[0021] According to even another embodiment of the present
invention, there is provided a method of killing a well. The method
generally includes contacting the above described well kill
additive with water or an aqueous solution to form a well kill
fluid. The method then includes injecting the well kill fluid into
the well bore. More specifically, the method includes substantially
reducing volumetric flow of a formation fluid across a wellbore
face into a wellbore penetrating a formation having a formation
matrix and containing said formation fluid below an earthen surface
by: providing a well kill additive comprising a dry mixture of
water soluble crosslinkable polymer, a crosslinking agent, and a
reinforcing material selected from among fibers and comminuted
plant materials; placing said partial gel in said wellbore at said
wellbore face, said partial gel which is placed at said wellbore
face does not significantly penetrate the formation matrix; forming
said nonflowing gel from said partial gel in said wellbore at said
wellbore face to substantially reduce said volumetric flow of said
formation fluid across said wellbore face into said wellbore,
thereby killing said well; and removing substantially all of said
nonflowing gel from said wellbore face to substantially restore the
volumetric flow of said formation fluid into said wellbore.
[0022] These and other embodiments of the present invention will
become apparent to those of skill in the art upon review of this
specification and claims.
DETAILED DESCRIPTION OF THE INVENTION
[0023] The present invention is a process employing a material
which prevents or minimizes the substantial flow of formation
fluids into the wellbore during the performance of conventional oil
field wellbore operations, such as drilling, completions, or
workovers, while simultaneously preventing or minimizing the
leakoff of wellbore fluids into the formation matrix. The material
employed in the present process comprises a continuous, nonflowing,
crosslinked, water-soluble, polymer gel.
[0024] The utility of the present process in oil field wellbore
operations is attributable to the specific composition of the kill
additive. The well kill additive of the present invention includes
polymer, cross-linking agent and either fibers or comminuted
particles of plant materials. In a preferred embodiment of the
present invention, the well kill additive is a dry mixture of
polymer, cross-linking agent and either fibers or comminuted
particles of plant materials.
[0025] When placed in a wellbore, the additive crosslinks to
completion forming a nonflowing polymer which is sufficiently
strong to effectively prevent or minimize fluid intrusion into the
wellbore, even under high formation fluid pressures and
sufficiently strong to effectively prevent or minimize excessive
leakoff of the polymer gel out of the wellbore, even in the
presence of significant voids in direct communication with the
wellbore. The polymer gel is nondamaging to the formation and
residual gel remaining in the wellbore is generally reversible if
desired.
[0026] Any suitable relative amounts of the polymer, crosslinking
agent and either fibers or comminuted particles of plant materials
may be utilized in the present invention provided that the desired
well kill results are achieved. Generally, the fibers or comminuted
particles will comprise in the range of about 1 to about 99 weight
percent, preferably in the range of about 25 to about 90 weight
percent, more preferably in the range of about 50 to about 80
weight percent, and even more preferably in the range of about 70
to about 75 weight percent, all based on the total with of the
polymer, fibers and particles. A suitable amount of crosslinking
agent is provided to reach the desired amount of crosslinking.
Suitable amounts of dispersants, retarders, accelerents, and other
additives may be provided as necessary or desired.
[0027] The polymer utilized in the practice of the present
invention is preferably water soluble and must be capable of being
pumped as a liquid and subsequently crosslinked in place to form a
substantially non-flowing crosslinked polymer which has sufficient
strength to withstand the pressures exerted on it. Moreover, it
must have a network structure capable of incorporating reinforcing
fibers.
[0028] While any suitable water soluble polymer may be utilized,
the preferred polymer utilized in the practice of the present
invention is a carboxylate-containing polymer. This preferred
carboxylate-containing polymer may be any crosslinkable, high
molecular weight, water-soluble, synthetic polymer or biopolymer
containing one or more carboxylate species.
[0029] For an example of suitable polymers and crosslinking agents,
and details regarding their making and use for well kill operation,
please see U.S. Pat. Nos. 4,947,935 and 4,995,461, both herein
incorporated by reference.
[0030] The average molecular weight of the carboxylate-containing
polymer utilized in the practice of the present invention is in the
range of about 10,000 to about 50,000,000, preferably in the range
of about 100,000 to about 20,000,000, and most preferably in the
range of about 200,000 to about 15,000,000.
[0031] Biopolymers useful in the present invention include
polysaccharides and modified polysaccharides. Nonlimiting examples
of biopolymers are xanthan gum, guar gum, carboxymethylcellulose,
o-carboxychitosans, hydroxyethylcellulose, hydroxypropylcellulose,
and modified starches. Non-limiting examples of useful synthetic
polymers include acrylamide polymers, such as polyacrylamide,
partially hydrolyzed polyacrylamide and terpolymers containing
acrylamide, acrylate, and a third species. As defined herein,
polyacrylamide (PA) is an acrylamide polymer having substantially
less than 1% of the acrylamide groups in the form of carboxylate
groups. Partially hydrolyzed polyacrylamide (PHPA) is an acrylamide
polymer having at least 1%, but not 100%, of the acrylamide groups
in the form of carboxylate groups. The acrylamide polymer may be
prepared according to any conventional method known in the art, but
preferably has the specific properties of acrylamide polymer
prepared according to the method disclosed by U.S. Pat. No. Re.
32,114 to Argabright et al incorporated herein by reference.
[0032] Any crosslinking agent suitable for use with the selected
polymer may be utilized in the practice of the present invention.
Preferably, the crosslinking agent utilized in the present
invention is a chromic carboxylate complex.
[0033] The term "complex" is defined herein as an ion or molecule
containing two or more interassociated ionic, radical or molecular
species. A complex ion as a whole has a distinct electrical charge
while a complex molecule is electrically neutral. The term "chromic
carboxylate complex" encompasses a single complex, mixtures of
complexes containing the same carboxylate species, and mixtures of
complexes containing differing carboxylate species.
[0034] The chromic carboxylate complex useful in the practice of
the present invention includes at least one or more electropositive
chromium III species and one or more electronegative carboxylate
species. The complex may advantageously also contain one or more
electronegative hydroxide and/or oxygen species. It is believed
that, when two or more chromium III species are present in the
complex, the oxygen or hydroxide species may help to bridge the
chromium III species. Each complex optionally contains additional
species which are not essential to the polymer crosslinking
function of the complex. For example, inorganic mono- and/or
divalent ions, which function merely to balance the electrical
charge of the complex, or one or more water molecules may be
associated with each complex. Non-limiting representative formulae
of such complexes include:
[Cr.sub.3(CH.sub.3CO.sub.2).sub.6 (OH).sub.2].sup.1+;
[Cr.sub.3(CH.sub.3CO.sub.2).sub.6(OH).sub.2
]NO.sub.3.6H.sub.2O;
[Cr.sub.3(CH.sub.3CO.sub.2).sub.6(OH).sub.2].sup.3+; and
[Cr.sub.3
(CH.sub.3CO.sub.2).sub.6(OH).sub.2](CH.sub.3CO.sub.2).sub.3.H.su-
b.2O.
[0035] "Trivalent chromium" and "chromic ion" are equivalent terms
encompassed by the term "chromium III" species as used herein.
[0036] The carboxylate species are advantageously derived from
water-soluble salts of carboxylic acids, especially low molecular
weight mono-basic acids. Carboxylate species derived from salts of
formic, acetic, propionic, and lactic acid, substituted derivatives
thereof and mixtures thereof are preferred. The preferred
carboxylate species include the following water-soluble species:
formate, acetate, propionate, lactate, substituted derivatives
thereof, and mixtures thereof. Acetate is the most preferred
carboxylate species. Examples of optional inorganic ions include
sodium, sulfate, nitrate and chloride ions.
[0037] A host of complexes of the type described above and their
method of preparation are well known in the leather tanning art.
These complexes are described in Shuttleworth and Russel, Journal
of the Society of Leather Trades' Chemists, "The Kinetics of Chrome
Tannage Part I.," United Kingdom, 1965, v. 49, p. 133-154; "Part
III.," United Kingdom, 1965, v. 49, p. 251-260; "Part IV.," United
Kingdom, 1965, v. 49, p. 261-268; and Von Erdman, Das Leder,
"Condensation of Mononuclear Chromium (III) Salts to Polynuclear
Compounds," Eduard Roether Verlag, Darmstadt Germany, 1963, v. 14,
p. 249; and incorporated herein by reference. Udy, Marvin J.,
Chromium. Volume 1: Chemistry of Chromium and its Compounds.
Reinhold Publishing Corp., N.Y., 1956, pp. 229-233; and Cotton and
Wilkinson, Advanced Inorganic Chemistry 3rd Ed., John Wiley and
Sons, Inc., N.Y., 1972, pp. 836-839, further describe typical
complexes which may be within the scope of the present invention
and are incorporated herein by reference. The present invention is
not limited to the specific complexes and mixtures thereof
described in the references, but may include others satisfying the
above-stated definition.
[0038] Salts of chromium and an inorganic monovalent anion, e.g.,
CrCl3, may also be combined with the crosslinking agent complex to
accelerate gelation of the polymer solution, as described in U.S.
Pat. No. 4,723,605 to Sydansk, which is incorporated herein by
reference.
[0039] The molar ratio of carboxylate species to chromium III in
the chromic carboxylate complexes used in the process of the
present invention is typically in the range of 1:1 to 3.9:1. The
preferred ratio is range of 2:1 to 3.9:1 and the most preferred
ratio is 2.5:1 to 3.5:1.
[0040] The additive of the present invention may comprise fibers or
comminuted particles of plant materials, and preferably comprises
comminuted particles of one or more plant materials.
[0041] Fibers suitable for use in the present invention are
selected from among hydrophilic and hydrophobic fibers.
Incorporation of hydrophobic fibers will require use of a suitable
wetting agent. Preferably, the fibers utilized in the present
invention comprise hydrophilic fibers, most preferably both
hydrophilic and hydrophobic fibers.
[0042] With respect to any particular fiber employed in the
practice of the present invention, it is believed that the longer
the fiber, the more difficult it is to be mixed uniformly in
solution. It is believed that fibers as long as 12,500 microns may
tend to aggregate and form clumps. The shorter the fiber, it is
believed the easier it is to mix in solution. On the other hand,
the shorter the fiber, the greater the quantity necessary to
provide the desired level of strength in a reinforced mature gel.
In general, the fibers utilized in the present invention will have
a length in the range of 100 microns to 3200 microns, preferable
100 microns to 1000 microns.
[0043] Non-limiting examples of suitable hydrophobic fibers include
nylon, rayon, hydrocarbon fibers and mixtures thereof.
[0044] Non-limiting examples of suitable hydrophilic fibers include
glass, cellulose, carbon, silicon, graphite, calcined petroleum
coke, cotton fibers, and mixtures thereof.
[0045] Non-limiting examples of comminuted particles of plant
materials suitable for use in the present invention include any
derived from: nut and seed shells or hulls such as those of peanut,
almond, brazil, cocoa bean, coconut, cotton, flax, grass, linseed,
maize, millet, oat, peach, peanut, rice, rye, soybean, sunflower,
walnut, wheat; various portions of rice including the rice tips,
rice straw and rice bran; crude pectate pulp; peat moss fibers;
flax; cotton; cotton linters; wool; sugar cane; paper; bagasse;
bamboo; corn stalks; various tree portions including sawdust, wood
or bark; straw; cork; dehydrated vegetable matter (suitably
dehydrated carbonhydrates such as citrus pulp, oatmeal, tapioca,
rice grains, potatoes, carrots, beets, and various grain sorghams);
whole ground corn cobs; or various plant portions the corn cob
light density pith core, the corn cob ground woody ring portion,
the corn cob coarse or fine chaff portion, cotton seed stems, flax
stems, wheat stems, sunflower seed stems, soybean stems, maize
stems, rye grass stems, millet stems, and various mixtures of these
materials.
[0046] Optionally, dispersant for comminuted plant material will be
utilized the in the range of about 1 to about 20 pounds, preferably
in the range of about 5 to about 10 pounds, and more preferably in
the range of about 7 to about 8 pounds of dispersant may be
utilized per pound of comminuted plant material. A non-limiting
example of a suitable dispersant is NaCl.
[0047] Preferred comminuted materials useful in the practice of the
present invention include those derived from peanuts, wood, paper
any portion of rice seed or plant, and any portion of corn
cobs.
[0048] These various materials can be comminuted to very fine
particle sizes by drying the products and using hammer mills,
cutter heads, air control mills or other comminution methods as is
well known to those of skill in the comminution art. Air
classification equipment or other means can be used for separation
of desired ranges of particle sizes using techniques well-known in
the comminution art.
[0049] Any suitable size of comminuted material may be utilized in
the present invention, along as such size produces results which
are desired. In most instances, the size range of the comminuted
materials utilized herein will range from below about 8 mesh
("mesh" as used herein refers to standard U.S. mesh), preferably
from about -65 mesh to about -100 mesh, and more preferably from
about -65 mesh to about -85 mesh. Specifically preferred particle
sizes for some materials are provided below.
[0050] Preferred mixtures of comminuted materials useful in the
practice of the present invention include a rice fraction and
peanut hulls; a rice fraction and wood fiber and/or almond hulls; a
rice fraction and a corn cob fraction, preferably a chaff portion;
and a corn cob fraction, preferably a pith or chaff portion, a rice
fraction, and at least one of wood fiber, nut shells, paper and
shredded cellophane.
[0051] Rice is commercially available in the form of rice hulls,
rice tips, rice straw and rice bran, as these various parts of the
rice plant are separated commercially and are widely available from
rice mills. Preferably, the size range of the rice fraction
utilized herein will range from below about 8 mesh ("mesh" as used
herein refers to standard U.S. mesh), preferably from about -65
mesh to about -100 mesh, and more preferably from about -65 mesh to
about -85 mesh.
[0052] After the corn kernels are removed, corn cobs consist of
four principle parts that are arranged concentrically. The central
portion is a very light density pith core, that is surrounded by a
woody ring, that in turn is surrounded by a coarse chaff portion,
that in turn is covered by a fine chaff portion. The coarse and
fine chaff portions form the sockets for anchoring the corn kernels
to the corncob. The normal methods of grinding corncobs produce a
mixture of all four parts enumerated above. It is possible,
however, to separate the woody ring material from the remainder of
the cob. The chaff portion of the corncob remaining after removal
of the woody ring material is known as "bees wings". In the present
invention, any of the pith or chaff portions("BPC") are the
preferred portions of the corn cob, with the chaff portions being
more preferred. A range of particle sizes of pith and chaff can be
obtained from comminution, but the size range smaller than about 8
mesh is suitable for this invention. Preferably, a particle size
distribution ranging from smaller than 8 mesh to smaller than 100
mesh is utilized.
[0053] Preferred woods for use as comminuted materials in the
present invention include any type of hard wood fiber, including
cedar fiber, oak fiber, pecan fiber and elm fiber. Preferably the
wood fiber comprises cedar fibers.
[0054] Preferred nut shells for use in the present invention
include pecan, walnut, and almond. Preferably, the nut shells
comprise at least one of pecan or walnut shells.
[0055] Preferred particle sizes for the wood fibers, nut shells,
paper and cellophane will generally range from about +10 mesh to
-100 mesh. An illustration of a nonlimiting particle size
distribution for these materials would include particles of +10
mesh, +20 mesh, +30 mesh, +50 mesh, +60 mesh, +100 mesh, and -100
mesh.
[0056] For one of the preferred comminuted plant mixtures
comprising a corn cob fraction, a rice fraction, and at least one
of wood fiber, nut shells, paper and shredded cellophane, the
mixture will generally comprise in the range of about 5 to about 95
weight percent rice, in the range of about 5 to about 95 weight
percent corncob pith or chaff, with the total of ground wood fiber,
ground nut shells, ground paper and shredded cellophane comprising
in the range of about 5 to about 95 weight percent (weight percent
based on the total weight of plant material in the mixture.
Preferred ranges are about 20 to about 75 weight percent rice,
about 5 to about 35 weight percent corncob pith or chaff, with the
total of ground wood fiber, ground nut shells, ground paper and
shredded cellophane comprising in the range of about 20 to about 75
weight percent. More preferred ranges are about 30 to about 50
weight percent rice, about 10 to about 30 weight percent corncob
pith and chaff, with the total of ground wood fiber, ground nut
shells, ground paper and shredded cellophane comprising in the
range of about 25 to about 50 weight percent.
[0057] As these comminuted materials are to be added to a water
base well kill fluid, a small amount of oil may optionally added to
the mixture. This optional oil is preferably added while the plant
materials are being mixed together. This mixing may take place in a
ribbon blender, where the oil in the required amount is applied by
a spray bar. The oil wets the particles and adds to their lubricity
while at the same time helping to control dust produced by the
mixing operation. A variety of oils may be utilized in the practice
of the present invention in concentrations generally ranging from
about 1 percent to about 5 percent by weight based on the total
weight of the mixture of comminuted materials, more preferably
ranging from about 1 percent to about 2 percent. A nonlimiting
example of a commercially available oil suitable for use in the
present invention includes ISOPAR V, available from Exxon
Corporation.
[0058] The various components of the present invention may be mixed
in any suitable order utilizing mixing techniques as known to those
in the art, including dry mixing of the various components prior to
addition to water, or alternatively, either or both of the polymer
and cross-linking agent may be utilized as a solution. Most
preferably, the various components are mixed in dry form, and then
contacted with water or aqueous solution to form a well kill fluid.
This well kill fluid is then injected into the well as is known in
the art.
[0059] The polymer employed in the kill treatment of the present
process should have sufficient strength when it sets up at the
wellbore face to substantially reduce or eliminate the volumetric
flow of formation fluid into the wellbore while the polymer does
not substantially leak off into the formation matrix. By
"substantially reduce" it is meant that the volumetric flow of
formation fluid into the wellbore prior to placement of the gel
therein is greater than the volumetric flow after placement of the
gel. To satisfy this requirement the strength of the polymer should
be sufficient to withstand the formation fluid pressure and the
hydrostatic overbalance pressure without substantially deforming or
fracturing. The formation fluid pressure is in many cases about
equal to the hydrostatic head of a column of formation fluid
wherein the column is equal in height to the formation depth at the
point where fluid flows into the wellbore. The polymer gel must
also have sufficient strength to prevent or minimize leakoff of
wellbore fluids into the formation throughout the oil field
wellbore operation.
[0060] The strength of the gel can be augmented at the
practitioner's option by the addition of inert solids suspended or
dispersed in the gel. Non-limiting examples of inert solids
include, crushed rock, glass beads, plastic or cellulosic fibers
and the like.
[0061] Once the well kill fluid is formulated, it is injected into
the wellbore as a completely gelled composition, or alternatively,
it may be injected as a partially gelled composition to allow
increase of viscosity over time.
[0062] The well is killed by placing the partial flowing gel at
faces across which formation fluid enters the wellbore. Placement
of the partial gel at the faces can be facilitated by the use of
mechanical zone isolation packers if desired. Within a
predetermined time period complete gelation occurs and the gel sets
up as a nonflowing gel, which substantially prevents or reduces the
flow of formation fluids into the wellbore.
[0063] A "partial gel" as referred to herein has at least one
chemically crosslinked site. The partial gel may or may not
manifest the physical properties of a crosslinked gel, but the
partial polymer gel is capable of further crosslinking to
completion in situ, resulting in a gel having the desired
properties without the addition of more crosslinking agent. The
partial gel preferably has sufficient viscosity and/or plugging
efficiency to substantially prevent or reduce gel leakoff into the
formation during or subsequent to its placement.
[0064] "Complete gelation" means that the gel composition is
nonflowing and is incapable of further crosslinking because one or
both of the required reactants in the initial solution are
consumed. Further crosslinking is only possible if either more
polymer, crosslinking agent, or both are added to the gel
composition.
[0065] The volume of gel injected into the wellbore is an amount
which is at least sufficient to cover the faces across which the
formation fluid enters the wellbore. Thus, the volume required is a
function of the wellbore configuration and the adjacent formation.
If the wellbore is a uniform borehole free of adjacent voids, a
relatively small volume of gel will be required to kill the well.
However, if the borehole is irregular with many voids in direct
communication therewith, much larger volumes of gel may be required
to kill the well. In any case the present process has utility in
both cased and uncased wellbores depending on the particular
operation it is complimenting.
[0066] Without being limited by theory, it is believed that the gel
functions in the kill treatment of the present invention by coating
faces and at least partially, if not entirely, filling voids, if
any are present, which are in direct communication with the
wellbore. In so doing, the gel plugs the faces, thereby preventing
the flow of fluids across them and out of the wellbore or voids.
The gel also prevents the leakoff of wellbore fluids through the
wellbore or voids into the formation matrix. Although it is not
always possible, it is preferable that the gel as used in the
present invention fills and plugs the voids proximal the wellbore
first, which blocks flow into and out of voids remote from the
wellbore. This obviates the need to fill and plug remote voids,
thereby advantageously limiting the required volume of treatment
material to practice the present invention.
[0067] The following definitions apply to the present invention.
"Plugging" is a substantial reduction in permeability. The term
"face" is the interface between a wellbore or void and the
formation matrix, i.e., the walls of the wellbore or the walls or
boundaries of voids in direct communication with the wellbore. The
"wellbore" is the bore hole formed by the drill bit in the
formation. "Voids" are not formed by the drill bit, but are
nevertheless anomalies having a permeability substantially equal to
that of the bore hole relative to that of the matrix. Voids include
fractures, fracture networks, caverns, vugs, cavities, washouts,
cobble packs, unconsolidated sands, and the like, which may be
proximal or which may extend far away from the wellbore. The
"matrix" is homogeneous, continuous, sedimentary material having a
permeability, which is substantially less than that of the wellbore
or voids. "Direct communication" means that the voids are not
separated from the wellbore by intervening matrix.
[0068] After the oil field wellbore operation is completed, the
well may be utilized for its intended purpose, i.e., recovery of
hydrocarbon fluids from the formation or injection of fluids into
the formation. Since the gel does not significantly penetrate the
formation matrix beyond about 1 cm from the wellbore face, the gel
is nondamaging to the formation matrix to the extent that it does
not substantially inhibit subsequent flow of fluids into or out of
the wellbore after it is removed therefrom. Even if the gel
unacceptably inhibits the flow of fluids, the problem can be
remedied by perforating the matrix beyond the layer of gel
penetration.
[0069] The present invention can be practiced using the additive as
a primary treatment material according to the manner set forth
above. In another embodiment of the invention, the additive is
employed in a remedial role after the failure of a conventional
well kill treatment. If one has attempted to kill a well using
large volumes of a conventional material, such as a heavy brine
containing a water-soluble uncrosslinked biopolymer, with little
apparent success, the conventional treatment is terminated and the
treatment process of the present invention is performed in the
manner described above to effectively kill the well. In any case
the well fluid treatment additive and fluid of the present
invention is most preferred for killing wells having significant
voids in direct communication with the wellbore, which would cause,
or already have caused, significant leakoff of conventional kill
fluids from the wellbore into the formation matrix.
[0070] The polymer gel used in the present invention is generally
maintained in the wellbore throughout the performance of the oil
field wellbore operation. The gel should be placed such that it
enables one to perform the desired operation in the wellbore
without substantially interfering with the operation. Once the oil
field wellbore operation is completed, it is usual to begin or
resume injection of fluids into the formation or production of
formation fluids from the wellbore, depending on whether the
wellbore is an injection or production wellbore. In most cases it
is desirable to remove the well kill additive from the wellbore
before injecting or producing fluids. The well kill additive may be
removed by drilling it out or any other conventional means.
[0071] Since the polymer gels employed in the process of the
present invention are generally reversible, removal of residual gel
from the wellbore after the completion of a particular wellbore
operation can also be accomplished by reversing the gel with a
conventional breaker, such as peroxides, hypochlorites or
persulfates. The breaker can be incorporated into the initial gel
composition at the surface to slowly break the gel over time or the
breaker can be placed in the wellbore separately to reverse the gel
on contact at the desired time after completion of the wellbore
operation.
[0072] While the illustrative embodiments of the invention have
been described with particularity, it will be understood that
various other modifications will be apparent to and can be readily
made by those skilled in the art without departing from the spirit
and scope of the invention. Accordingly, it is not intended that
the scope of the claims appended hereto be limited to the examples
and descriptions set forth herein but rather that the claims be
construed as encompassing all the features of patentable novelty
which reside in the present invention, including all features which
would be treated as equivalents thereof by those skilled in the art
to which this invention pertains.
* * * * *