U.S. patent application number 17/666720 was filed with the patent office on 2022-05-26 for silane-functionalized polyalkyleneimine clay stabilizer for treatment of subterranean formations.
This patent application is currently assigned to Halliburton Energy Services, Inc.. The applicant listed for this patent is Halliburton Energy Services, Inc.. Invention is credited to Denise Nicole Benoit, Tatyana V. Khamatnurova, Gladys Rocio Montenegro-Galindo.
Application Number | 20220162383 17/666720 |
Document ID | / |
Family ID | |
Filed Date | 2022-05-26 |
United States Patent
Application |
20220162383 |
Kind Code |
A1 |
Khamatnurova; Tatyana V. ;
et al. |
May 26, 2022 |
Silane-Functionalized Polyalkyleneimine Clay Stabilizer for
Treatment of Subterranean Formations
Abstract
Various embodiments disclosed relate to a silane-functionalized
polyalkyleneimine (PAI) clay stabilizer for treatment of
subterranean formations. In various embodiments, the present
invention provides a method of treating a subterranean formation.
The method can include placing in the subterranean formation a
silane-functionalized PAI clay stabilizer.
Inventors: |
Khamatnurova; Tatyana V.;
(Houston, TX) ; Montenegro-Galindo; Gladys Rocio;
(Kingwood, TX) ; Benoit; Denise Nicole; (Houston,
TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Halliburton Energy Services, Inc. |
Houston |
TX |
US |
|
|
Assignee: |
Halliburton Energy Services,
Inc.
Houston
TX
|
Appl. No.: |
17/666720 |
Filed: |
February 8, 2022 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15762068 |
Mar 21, 2018 |
11279801 |
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PCT/US2015/055990 |
Oct 16, 2015 |
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17666720 |
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International
Class: |
C08G 73/02 20060101
C08G073/02; C09K 8/035 20060101 C09K008/035; C09K 8/80 20060101
C09K008/80; C09K 8/467 20060101 C09K008/467; C09K 8/52 20060101
C09K008/52; C09K 8/60 20060101 C09K008/60; C09K 8/64 20060101
C09K008/64; C09K 8/68 20060101 C09K008/68; C09K 8/72 20060101
C09K008/72; C09K 8/74 20060101 C09K008/74; C09K 8/82 20060101
C09K008/82; C09K 8/88 20060101 C09K008/88; E21B 41/00 20060101
E21B041/00 |
Claims
1. A composition comprising a silane-functionalized
polyalkyleneimine (PAI) clay stabilizer, wherein the composition is
active to stabilize a clay of a subterranean clay formation against
clay swelling, clay migration, and fines generation in the
subterranean formation via covalent silyl bond formation and
electrostatic interaction between the clay and the
silane-functionalized PAI clay stabilizer.
2. The composition of claim 1, wherein the silane-functionalized
PAI clay stabilizer is a polymer comprising a repeating unit having
the following structure: ##STR00039## wherein at each occurrence of
R.sup.1 and D in the same repeating unit, R.sup.1 is independently
selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and --(X).sub.m--
CH.sub.2--CHE-N(R.sup.2).sub.2, and D is H, or R.sup.1 and D
together in the same repeating unit form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.1 is bound,
at each occurrence, X is independently selected from the group
consisting of --(CH.sub.2).sub.2--O--, --(CH.sub.2).sub.3--O--,
--(CH.sub.2).sub.2--S--, --(CH.sub.2).sub.3--S--, and a
--(C.sub.1-10)alkylene-, at each occurrence, m is about 0 to about
10, at each occurrence, L.sup.1 is a substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbylene interrupted by 0, 1, 2, or 3
groups independently selected from --O--, --S--, and substituted or
unsubstituted --NH--, at each occurrence, R.sup.A is independently
selected from --O--R.sup.B, --H, and --R.sup.B, wherein at least
one R.sup.A of each --Si--(R.sup.A).sub.3 is --O--R.sup.B, at each
occurrence, R.sup.B is independently substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl, at each occurrence of R.sup.2 and E
in the same R.sup.1 or in the same R.sup.3, R.sup.2 is
independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHF--N(R.sup.3).sub.2, and E is H, or
R.sup.2 and E together in the same R.sup.1 or in the same R.sup.3
form a (C.sub.1-C.sub.10)heterocycle with the N to which R.sup.2 is
bound, at each occurrence of R.sup.3 and F in the same R.sup.2,
R.sup.3 is independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and F is H, or R.sup.3
and F together in the same R.sup.2 form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.3 is bound,
at one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, and R.sup.3 in the silane-functionalized PAI clay
stabilizer molecule is a silicon-containing group, and each amine
group is independently in the form of a neutral amine or a
protonated cationic amine.
3. The composition of claim 2, wherein the silane-functionalized
PAI clay stabilizer has the structure: ##STR00040## wherein at each
occurrence of R.sup.4 in an end group not including G, R.sup.4 is
independently selected from the group consisting of --H and
-L.sup.1-Si--(R.sup.A).sub.3, at each occurrence of R.sup.4 and G
in the same end group, R.sup.4 is independently selected from the
group consisting of --H and -L.sup.1-Si--(R.sup.A).sub.3 and G is
H, or R.sup.4 and G together in the same end group form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.4 is bound,
n is about 2 to about 1,000,000, and each amine group is
independently in the form of a neutral amine or a protonated
cationic amine.
4. The composition of claim 2, wherein the silane-functionalized
PAI clay stabilizer has the structure: ##STR00041## wherein at each
occurrence, R.sup.4 is independently selected from the group
consisting of --H and -L.sup.1-Si--(R.sup.A).sub.3, n is about 2 to
about 1,000,000, and each amine group is independently in the form
of a neutral amine or a protonated cationic amine.
5. The composition of claim 1, wherein the silane-functionalized
PAI clay stabilizer is a polymer comprising a repeating unit having
the following structure: ##STR00042## wherein at each occurrence,
R.sup.1 is independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, at each occurrence, L.sup.1
is a substituted or unsubstituted (C.sub.1-C.sub.20)hydrocarbylene
interrupted by 0, 1, 2, or 3 groups independently selected from
--O--, --S--, and substituted or unsubstituted --NH--, at each
occurrence, R.sup.A is independently selected from --O--R.sup.B,
--H, and --R.sup.B, wherein at least one R.sup.A of each
--Si--(R.sup.A).sub.3 is --O--R.sup.B, at each occurrence, R.sup.B
is independently substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl, at each occurrence, R.sup.2 is
independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2, at each occurrence, R.sup.3
is independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, at one or more occurrences,
at least one group selected from R.sup.1, R.sup.2, and R.sup.3 in
the silane-functionalized clay stabilizer PAI molecule is a
silicon-containing group, and each amine group is independently in
the form of a neutral amine or a protonated cationic amine.
6. The composition of claim 1, wherein the silane-functionalized
PAI clay stabilizer has the structure ##STR00043## wherein at each
occurrence, R.sup.1 is independently selected from the group
consisting of --H,
--CH.sub.2--CH(OH)--(C.sub.1-C.sub.5)alkylene-O--(C.sub.1-C.sub.10)alkyle-
ne-Si(O--(C.sub.1-C.sub.10)alkyl).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, wherein at each occurrence,
each (C.sub.1-C.sub.10)alkylene, (C.sub.1-C.sub.8)alkylene, and
(C.sub.1-C.sub.10)alkyl is independently selected, at each
occurrence, R.sup.2 is independently selected from the group
consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2, at each occurrence, R.sup.3
is independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, at each occurrence, R.sup.4
is independently selected from the group consisting of --H and
-L.sup.1-Si--(R.sup.A).sub.3, at one or more occurrences, at least
one group selected from R.sup.1, R.sup.2, R.sup.3, and R.sup.4 in
the silane-functionalized clay stabilizer PAI molecule is a
silicon-containing group, n is about 2 to about 1,000,000, and each
amine group is independently in the form of a neutral amine or a
protonated cationic amine.
7. The composition of claim 1, wherein the silane-functionalized
PAI clay stabilizer is prepared by: forming a mixture comprising a
silane-functionalized epoxide and a PAI; and allowing the mixture
to react to form the silane-functionalized PAI clay stabilizer.
8. The composition of claim 7, wherein the PAI is a polymer
comprising a repeating unit having the structure: ##STR00044##
wherein at each occurrence of R.sup.1 and D in the same repeating
unit, R.sup.1 is independently selected from the group consisting
of --H and --(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and D is H,
or R.sup.1 and D together in the same repeating unit form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.1 is bound,
at each occurrence, X is independently selected from the group
consisting of --(CH.sub.2).sub.2--O--, --(CH.sub.2).sub.3--O--,
--(CH.sub.2).sub.2--S--, --(CH.sub.2).sub.3--S--, and a
--(C.sub.1-10)alkylene-, at each occurrence, m is about 0 to about
10, at each occurrence of R.sup.2 and E in the same R.sup.1 or in
the same R.sup.3, R.sup.2 is independently selected from the group
consisting of --H and --(X).sub.m--CH.sub.2--CHF--N(R.sup.3).sub.2,
and E is H, or R.sup.2 and E together in the same R.sup.1 or in the
same R.sup.3 form a (C.sub.1-C.sub.10)heterocycle with the N to
which R.sup.2 is bound, at each occurrence of R.sup.3 and F in the
same R.sup.2, R.sup.3 is independently selected from the group
consisting of --H and --(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2,
and F is H, or R.sup.3 and F together in the same R.sup.2 form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.3 is bound,
and each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
9. The composition of claim 8, wherein the PAI is PEI, wherein m is
0, D, E, and F are H, wherein the PEI is a polymer comprising a
repeating unit having the structure: ##STR00045## wherein at each
occurrence, R.sup.1 is independently selected from the group
consisting of --H and --CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, at
each occurrence, R.sup.2 is independently selected from the group
consisting of --H, and --CH.sub.2--CH.sub.2--N(R.sup.3).sub.2, at
each occurrence, R.sup.3 is independently selected from the group
consisting of --H, and --CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, and
each amine group is independently in the form of a neutral amine or
a protonated cationic amine.
10. The composition of claim 9, wherein the PEI has the structure:
##STR00046## wherein n is about 2 to about 1,000,000, and each
amine group is independently in the form of a neutral amine or a
protonated cationic amine.
11. The composition of claim 1, wherein the silane-functionalized
PAI clay stabilizer has the structure: ##STR00047## wherein at each
occurrence, R.sup.1 is independently selected from the group
consisting of --H,
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).-
sub.3, and --CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, at each
occurrence, R.sup.2 is independently selected from the group
consisting of --H,
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).sub.3,
and --CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, at each occurrence,
R.sup.3 is independently selected from the group consisting of --H,
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).sub.3,
and --CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, at each occurrence,
R.sup.4 is independently selected from the group consisting of --H
and
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).sub.3,
at one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 in the silane-functionalized
PAI clay stabilizer molecule is a silicon-containing group, n is
about 2 to about 1,000,000, and each amine group is independently
in the form of a neutral amine or a protonated cationic amine.
12. The composition of claim 1, wherein the composition further
comprises a proppant, a resin-coated proppant, or a combination
thereof.
13. The composition of claim 1, wherein the clay stabilizer
composition is dispersed or dissolved in a carrier fluid.
14. The composition of claim 1, wherein the composition further
comprises a secondary clay stabilizer.
15. The composition of claim 14, wherein the secondary clay
stabilizer comprises potassium chloride, a non-polymeric ionic
liquid, an inorganic phosphate, a polyalkoxy diamine or a salt
thereof, choline or a choline derivative, an oligomethylene diamine
or a salt thereof, an addition product of carboxymethyl cellulose
and an organic amine, 1,2-cyclohexanediamine or a salt thereof, a
salt of a phosphoric acid ester of an oxyalkylated polyol, a
combination of a partially hydrolyzed acrylic copolymer potassium
chloride and polyanionic cellulose, a quaternary ammonium compound,
a polymer based on dialkyl aminoalkyl methacrylate, an aqueous
solution containing a polymer with hydrophilic and hydrophobic
groups, a reaction product of a polyhydroxyalkane and an alkylene
oxide, or a combination thereof.
16. A composition comprising a silane-functionalized epoxide and a
PAI, wherein the silane-functionalized epoxide and the PAI are
reactable to form a silane-functionalized PAI clay stabilizer; and
the composition is active to stabilize a clay of a subterranean
clay formation against clay swelling, clay migration, and fines
generation in the subterranean formation via covalent silyl bond
formation and electrostatic interaction between the clay and the
silane-functionalized PAI clay stabilizer.
17. The composition of claim 16, wherein the composition comprises
a pH of about 8 to about 10.
18. The composition of claim 16, wherein the silane-functionalized
epoxide has the structure: ##STR00048## wherein at each occurrence,
L.sup.1A is a substituted or unsubstituted
(C.sub.1-C.sub.20)alkylene interrupted by --O--, at each
occurrence, R.sup.A is independently selected from --O--R.sup.B,
--H, and --R.sup.B, wherein at least one R.sup.A of each
--Si--(R.sup.A).sub.3 is --O--R.sup.B, and at each occurrence,
R.sup.B is independently substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl.
19. The composition of claim 16, wherein the silane-functionalized
epoxide has the structure: ##STR00049##
20. A system comprising: a tubular disposed in a subterranean
formation; and a pump configured to pump a clay stabilizer
composition comprising a silane-functionalized polyalkyleneimine
(PAI) clay stabilizer in the subterranean formation through the
tubular, wherein the clay stabilizer composition is active to
stabilize a clay of a subterranean clay formation against clay
swelling, clay migration, and fines generation in the subterranean
formation via covalent silyl bond formation and electrostatic
interaction between the clay and the silane-functionalized PAI clay
stabilizer.
Description
BACKGROUND
[0001] Swelling clays can be a major mechanism of formation damage
due to loss of mobility of hydrocarbon fluids in the formation.
When clays encounter foreign water, such as well-treatment fluids
or produced water, they can swell, causing a loss of permeability.
The swelling can cause portions of the clay and adjacent fines to
become mobile within the production stream and, too frequently,
encounter constrictions in capillaries, where they can bridge off
the capillaries and severely diminish the flow rate of hydrocarbons
to the wellbore. Sometimes the loss of permeability observed is due
to clay swelling without migration, but often clay swelling is
accompanied by migration of clay and other fines. Non-swelling
clays may also respond to the foreign water and begin to
migrate.
[0002] Stabilization of formation materials against the swelling
and migration of clay and the generation of fines is necessary in
subterranean treatments such as hydraulic fracturing, gravel
packing, and any activity where aqueous fluid comes in contact with
water-sensitive clay-containing formation materials. However, many
clay stabilizers are expensive, less effective than desirable,
environmentally undesirable due to toxicity or lack of
biodegradability, and can cause damage to subterranean
formations.
BRIEF DESCRIPTION OF THE FIGURES
[0003] The drawings illustrate generally, by way of example, but
not by way of limitation, various embodiments discussed in the
present document.
[0004] FIG. 1 illustrates a drilling assembly, in accordance with
various embodiments.
[0005] FIG. 2 illustrates a system or apparatus for delivering a
composition to a subterranean formation, in accordance with various
embodiments.
[0006] FIG. 3 illustrates a reaction of PEI with
3-glycidoxypropyltrimethoxysilane, in accordance with various
embodiments.
[0007] FIG. 4 illustrates proposed mechanisms for interaction of a
silane-functionalized PEI clay stabilizer with clay surfaces, in
accordance with various embodiments.
[0008] FIG. 5 illustrates the formation damage measured during a
fines generation test and a clay swelling test for various clay
stabilizers, in accordance with various embodiments.
DETAILED DESCRIPTION OF THE INVENTION
[0009] Reference will now be made in detail to certain embodiments
of the disclosed subject matter, examples of which are illustrated
in part in the accompanying drawings. While the disclosed subject
matter will be described in conjunction with the enumerated claims,
it will be understood that the exemplified subject matter is not
intended to limit the claims to the disclosed subject matter.
[0010] In this document, values expressed in a range format should
be interpreted in a flexible manner to include not only the
numerical values explicitly recited as the limits of the range, but
also to include all the individual numerical values or sub-ranges
encompassed within that range as if each numerical value and
sub-range is explicitly recited. For example, a range of "about
0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to
include not just about 0.1% to about 5%, but also the individual
values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to
0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The
statement "about X to Y" has the same meaning as "about X to about
Y," unless indicated otherwise. Likewise, the statement "about X,
Y, or about Z" has the same meaning as "about X, about Y, or about
Z," unless indicated otherwise.
[0011] In this document, the terms "a," "an," or "the" are used to
include one or more than one unless the context clearly dictates
otherwise. The term "or" is used to refer to a nonexclusive "or"
unless otherwise indicated. The statement "at least one of A and B"
has the same meaning as "A, B, or A and B." In addition, it is to
be understood that the phraseology or terminology employed herein,
and not otherwise defined, is for the purpose of description only
and not of limitation. Any use of section headings is intended to
aid reading of the document and is not to be interpreted as
limiting; information that is relevant to a section heading may
occur within or outside of that particular section. A comma can be
used as a delimiter or digit group separator to the left or right
of a decimal mark; for example, "0.000,1" is equivalent to
"0.0001."
[0012] In the methods described herein, the acts can be carried out
in any order without departing from the principles of the
invention, except when a temporal or operational sequence is
explicitly recited. Furthermore, specified acts can be carried out
concurrently unless explicit claim language recites that they be
carried out separately. For example, a claimed act of doing X and a
claimed act of doing Y can be conducted simultaneously within a
single operation, and the resulting process will fall within the
literal scope of the claimed process.
[0013] The term "about" as used herein can allow for a degree of
variability in a value or range, for example, within 10%, within
5%, or within 1% of a stated value or of a stated limit of a range,
and includes the exact stated value or range.
[0014] The term "substantially" as used herein refers to a majority
of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%,
96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999%
or more, or 100%.
[0015] The term "organic group" as used herein refers to any
carbon-containing functional group. Examples can include an
oxygen-containing group such as an alkoxy group, aryloxy group,
aralkyloxy group, oxo(carbonyl) group; a carboxyl group including a
carboxylic acid, carboxylate, and a carboxylate ester; a
sulfur-containing group such as an alkyl and aryl sulfide group;
and other heteroatom-containing groups. Non-limiting examples of
organic groups include OR, OOR, OC(O)N(R).sub.2, CN, CF.sub.3,
OCF.sub.3, R, C(O), methylenedioxy, ethylenedioxy, N(R).sub.2, SR,
SOR, SO.sub.2R, SO.sub.2N(R).sub.2, SO.sub.3R, C(O)R, C(O)C(O)R,
C(O)CH.sub.2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R).sub.2,
OC(O)N(R).sub.2, C(S)N(R).sub.2, (CH.sub.2).sub.0-2N(R)C(O)R,
(CH.sub.2).sub.0-2N(R)N(R).sub.2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR,
N(R)N(R)CON(R).sub.2, N(R)SO.sub.2R, N(R)SO.sub.2N(R).sub.2,
N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R).sub.2,
N(R)C(S)N(R).sub.2, N(COR)COR, N(OR)R, C(.dbd.NH)N(R).sub.2,
C(O)N(OR)R, C(.dbd.NOR)R, and substituted or unsubstituted
(C.sub.1-C.sub.100)hydrocarbyl, wherein R can be hydrogen (in
examples that include other carbon atoms) or a carbon-based moiety,
and wherein the carbon-based moiety can itself be substituted or
unsubstituted.
[0016] The term "substituted" as used herein in conjunction with a
molecule or an organic group as defined herein refers to the state
in which one or more hydrogen atoms contained therein are replaced
by one or more non-hydrogen atoms. The term "functional group" or
"substituent" as used herein refers to a group that can be or is
substituted onto a molecule or onto an organic group. Examples of
substituents or functional groups include, but are not limited to,
a halogen (e.g., F, Cl, Br, and I); an oxygen atom in groups such
as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy
groups, oxo(carbonyl) groups, carboxyl groups including carboxylic
acids, carboxylates, and carboxylate esters; a sulfur atom in
groups such as thiol groups, alkyl and aryl sulfide groups,
sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide
groups; a nitrogen atom in groups such as amines, hydroxyamines,
nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines;
and other heteroatoms in various other groups. Non-limiting
examples of substituents that can be bonded to a substituted carbon
(or other) atom include F, Cl, Br, I, OR, OC(O)N(R).sub.2, CN, NO,
NO.sub.2, ONO.sub.2, azido, CF.sub.3, OCF.sub.3, R, O (oxo), S
(thiono), C(O), S(O), methylenedioxy, ethylenedioxy, N(R).sub.2,
SR, SOR, SO.sub.2R, SO.sub.2N(R).sub.2, SO.sub.3R, C(O)R,
C(O)C(O)R, C(O)CH.sub.2C(O)R, C(S)R, C(O)OR, OC(O)R,
C(O)N(R).sub.2, OC(O)N(R).sub.2, C(S)N(R).sub.2,
(CH.sub.2).sub.0-2N(R)C(O)R, (CH.sub.2).sub.0-2N(R)N(R).sub.2,
N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R).sub.2, N(R)SO.sub.2R,
N(R)SO.sub.2N(R).sub.2, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R,
N(R)C(O)N(R).sub.2, N(R)C(S)N(R).sub.2, N(COR)COR, N(OR)R,
C(.dbd.NH)N(R).sub.2, C(O)N(OR)R, and C(.dbd.NOR)R, wherein R can
be hydrogen or a carbon-based moiety; for example, R can be
hydrogen, (C.sub.1-C.sub.100)hydrocarbyl, alkyl, acyl, cycloalkyl,
aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl; or
wherein two R groups bonded to a nitrogen atom or to adjacent
nitrogen atoms can together with the nitrogen atom or atoms form a
heterocyclyl.
[0017] The term "alkyl" as used herein refers to straight chain and
branched alkyl groups and cycloalkyl groups having from 1 to 40
carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbons or, in
some embodiments, from 1 to 8 carbon atoms. Examples of straight
chain alkyl groups include those with from 1 to 8 carbon atoms such
as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl,
and n-octyl groups. Examples of branched alkyl groups include, but
are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl,
neopentyl, isopentyl, and 2,2-dimethylpropyl groups. As used
herein, the term "alkyl" encompasses n-alkyl, isoalkyl, and
anteisoalkyl groups as well as other branched chain forms of alkyl.
Representative substituted alkyl groups can be substituted one or
more times with any of the groups listed herein, for example,
amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen
groups.
[0018] The term "alkenyl" as used herein refers to straight and
branched chain and cyclic alkyl groups as defined herein, except
that at least one double bond exists between two carbon atoms.
Thus, alkenyl groups have from 2 to 40 carbon atoms, or 2 to about
20 carbon atoms, or 2 to 12 carbon atoms or, in some embodiments,
from 2 to 8 carbon atoms. Examples include, but are not limited to
vinyl, --CH.dbd.CH(CH.sub.3), --CH.dbd.C(CH.sub.3).sub.2,
--C(CH.sub.3).dbd.CH.sub.2, --C(CH.sub.3).dbd.CH(CH.sub.3),
--C(CH.sub.2CH.sub.3).dbd.CH.sub.2, cyclohexenyl, cyclopentenyl,
cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl among
others.
[0019] The term "acyl" as used herein refers to a group containing
a carbonyl moiety wherein the group is bonded via the carbonyl
carbon atom. The carbonyl carbon atom is bonded to a hydrogen
forming a "formyl" group or is bonded to another carbon atom, which
can be part of an alkyl, aryl, aralkyl cycloalkyl, cycloalkylalkyl,
heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group
or the like. An acyl group can include 0 to about 12, 0 to about
20, or 0 to about 40 additional carbon atoms bonded to the carbonyl
group. An acyl group can include double or triple bonds within the
meaning herein. An acryloyl group is an example of an acyl group.
An acyl group can also include heteroatoms within the meaning
herein. A nicotinoyl group (pyridyl-3-carbonyl) is an example of an
acyl group within the meaning herein. Other examples include
acetyl, benzoyl, phenylacetyl, pyridylacetyl, cinnamoyl, and
acryloyl groups and the like. When the group containing the carbon
atom that is bonded to the carbonyl carbon atom contains a halogen,
the group is termed a "haloacyl" group. An example is a
trifluoroacetyl group.
[0020] The term "aryl" as used herein refers to cyclic aromatic
hydrocarbon groups that do not contain heteroatoms in the ring.
Thus aryl groups include, but are not limited to, phenyl, azulenyl,
heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl,
triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl,
anthracenyl, and naphthyl groups. In some embodiments, aryl groups
contain about 6 to about 14 carbons in the ring portions of the
groups. Aryl groups can be unsubstituted or substituted, as defined
herein. Representative substituted aryl groups can be
mono-substituted or substituted more than once, such as, but not
limited to, a phenyl group substituted at any one or more of 2-,
3-, 4-, 5-, or 6-positions of the phenyl ring, or a naphthyl group
substituted at any one or more of 2- to 8-positions thereof.
[0021] The term "heterocyclyl" or "heterocycle" as used herein
refers to aromatic and non-aromatic ring compounds containing three
or more ring members, of which one or more is a heteroatom such as,
but not limited to, N, O, and S. Thus, a heterocyclyl can be a
cycloheteroalkyl, or a heteroaryl, or if polycyclic, any
combination thereof. In some embodiments, heterocyclyl groups
include 3 to about 20 ring members, whereas other such groups have
3 to about 15 ring members. A heterocyclyl group designated as a
C.sub.2-heterocyclyl can be a 5-ring with two carbon atoms and
three heteroatoms, a 6-ring with two carbon atoms and four
heteroatoms and so forth. Likewise a C.sub.4-heterocyclyl can be a
5-ring with one heteroatom, a 6-ring with two heteroatoms, and so
forth. The number of carbon atoms plus the number of heteroatoms
equals the total number of ring atoms. A heterocyclyl ring can also
include one or more double bonds. A heteroaryl ring is an
embodiment of a heterocyclyl group. The phrase "heterocyclyl group"
includes fused ring species including those that include fused
aromatic and non-aromatic groups. For example, a dioxolanyl ring
and a benzdioxolanyl ring system (methylenedioxyphenyl ring system)
are both heterocyclyl groups within the meaning herein. The phrase
also includes polycyclic ring systems containing a heteroatom such
as, but not limited to, quinuclidyl. Heterocyclyl groups can be
unsubstituted, or can be substituted as discussed herein.
Heterocycle groups include, but are not limited to, pyrrolidine,
piperidine, piperazine, morpholine, pyrrole, pyrazole, triazole,
tetrazole, oxazole, isoxazole, thiazole, pyridine, thiophene,
benzothiophene, benzofurane, dihydrobenzofurane, indole,
dihydroindole, azaindole, indazole, benzimidazole,
azabenzimidazole, benzoxazole, benzothiazole, benzothiadiazole,
imidazopyridine, isoxazolopyridine, thianaphthalene, purine,
xanthine, adenine, guanine, quinoline, isoquinoline,
tetrahydroquinoline, quinoxaline, and quinazoline groups.
Representative substituted heterocyclyl groups can be
mono-substituted or substituted more than once, such as, but not
limited to, piperidinyl or quinolinyl groups, which are 2-, 3-, 4-,
5-, or 6-substituted, or disubstituted with groups such as those
listed herein.
[0022] The term "alkoxy" as used herein refers to an oxygen atom
connected to an alkyl group, including a cycloalkyl group, as are
defined herein. Examples of linear alkoxy groups include but are
not limited to methoxy, ethoxy, propoxy, butoxy, pentyloxy,
hexyloxy, and the like. Examples of branched alkoxy include but are
not limited to isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy,
isohexyloxy, and the like. Examples of cyclic alkoxy include but
are not limited to cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,
cyclohexyloxy, and the like. An alkoxy group can include about 1 to
about 12, about 1 to about 20, or about 1 to about 40 carbon atoms
bonded to the oxygen atom, and can further include double or triple
bonds, and can also include heteroatoms. For example, an allyloxy
group or a methoxyethoxy group is also an alkoxy group within the
meaning herein, as is a methylenedioxy group in a context where two
adjacent atoms of a structure are substituted therewith.
[0023] The term "amine" as used herein refers to primary,
secondary, and tertiary amines having, e.g., the formula
N(group).sub.3 wherein each group can independently be H or non-H,
such as alkyl, aryl, and the like. Amines include but are not
limited to R--NH.sub.2, for example, alkylamines, arylamines,
alkylarylamines; R.sub.2NH wherein each R is independently
selected, such as dialkylamines, diarylamines, aralkylamines,
heterocyclylamines and the like; and R.sub.3N wherein each R is
independently selected, such as trialkylamines, dialkylarylamines,
alkyldiarylamines, triarylamines, and the like. The term "amine"
also includes ammonium ions as used herein.
[0024] The term "amino group" as used herein refers to a
substituent of the form --NH.sub.2, --NHR, --NR.sub.2,
--NR.sub.3.sup.+, wherein each R is independently selected, and
protonated forms of each, except for --NR.sub.3.sup.+, which cannot
be protonated. Accordingly, any compound substituted with an amino
group can be viewed as an amine. An "amino group" within the
meaning herein can be a primary, secondary, tertiary, or quaternary
amino group. An "alkylamino" group includes a monoalkylamino,
dialkylamino, and trialkylamino group.
[0025] The terms "halo," "halogen," or "halide" group, as used
herein, by themselves or as part of another substituent, mean,
unless otherwise stated, a fluorine, chlorine, bromine, or iodine
atom.
[0026] The term "haloalkyl" group, as used herein, includes
mono-halo alkyl groups, poly-halo alkyl groups wherein all halo
atoms can be the same or different, and per-halo alkyl groups,
wherein all hydrogen atoms are replaced by halogen atoms, such as
fluoro. Examples of haloalkyl include trifluoromethyl,
1,1-dichloroethyl, 1,2-dichloroethyl,
1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.
[0027] The term "hydrocarbon" or "hydrocarbyl" as used herein
refers to a molecule or functional group, respectively, that
includes carbon and hydrogen atoms. The term can also refer to a
molecule or functional group that normally includes both carbon and
hydrogen atoms but wherein all the hydrogen atoms are substituted
with other functional groups. A hydrocarbyl group can be a
functional group derived from a straight chain, branched, or cyclic
hydrocarbon, and can be alkyl, alkenyl, alkynyl, aryl, cycloalkyl,
acyl, or any combination thereof. Hydrocarbyl groups can be shown
as (C.sub.a-C.sub.b)hydrocarbyl, wherein a and b are positive
integers and mean having any of a to b number of carbon atoms. For
example, (C.sub.1-C.sub.4)hydrocarbyl means the hydrocarbyl group
can be methyl (C.sub.1), ethyl (C.sub.2), propyl (C.sub.3), or
butyl (C.sub.4), and (C.sub.0-C.sub.b)hydrocarbyl means in certain
embodiments there is no hydrocarbyl group.
[0028] The term "solvent" as used herein refers to a liquid that
can dissolve a solid, liquid, or gas. Non-limiting examples of
solvents are silicones, organic compounds, water, alcohols, ionic
liquids, and supercritical fluids.
[0029] The term "number-average molecular weight" (M.sub.n) as used
herein refers to the ordinary arithmetic mean of the molecular
weight of individual molecules in a sample. It is defined as the
total weight of all molecules in a sample divided by the total
number of molecules in the sample. Experimentally, M.sub.n is
determined by analyzing a sample divided into molecular weight
fractions of species i having n.sub.i molecules of molecular weight
M.sub.i through the formula
M.sub.n=.SIGMA.M.sub.in.sub.i/.SIGMA.n.sub.i. The M.sub.n can be
measured by a variety of well-known methods including gel
permeation chromatography, spectroscopic end group analysis, and
osmometry. If unspecified, molecular weights of polymers given
herein are number-average molecular weights.
[0030] The term "weight-average molecular weight" as used herein
refers to Mw, which is equal to
.SIGMA.M.sub.in.sub.i/.SIGMA.M.sub.in.sub.i, where n.sub.i is the
number of molecules of molecular weight M.sub.i. In various
examples, the weight-average molecular weight can be determined
using light scattering, small angle neutron scattering, X-ray
scattering, and sedimentation velocity.
[0031] The term "room temperature" as used herein refers to a
temperature of about 15.degree. C. to 28.degree. C.
[0032] The term "standard temperature and pressure" as used herein
refers to 20.degree. C. and 101 kPa.
[0033] As used herein, "degree of polymerization" is the number of
repeating units in a polymer.
[0034] As used herein, the term "polymer" refers to a molecule
having at least one repeating unit and can include copolymers.
[0035] The term "copolymer" as used herein refers to a polymer that
includes at least two different repeating units. A copolymer can
include any suitable number of repeating units.
[0036] The term "downhole" as used herein refers to under the
surface of the earth, such as a location within or fluidly
connected to a wellbore.
[0037] As used herein, the term "drilling fluid" refers to fluids,
slurries, or muds used in drilling operations downhole, such as
during the formation of the wellbore.
[0038] As used herein, the term "stimulation fluid" refers to
fluids or slurries used downhole during stimulation activities of
the well that can increase the production of a well, including
perforation activities. In some examples, a stimulation fluid can
include a fracturing fluid or an acidizing fluid.
[0039] As used herein, the term "clean-up fluid" refers to fluids
or slurries used downhole during clean-up activities of the well,
such as any treatment to remove material obstructing the flow of
desired material from the subterranean formation. In one example, a
clean-up fluid can be an acidification treatment to remove material
formed by one or more perforation treatments. In another example, a
clean-up fluid can be used to remove a filter cake.
[0040] As used herein, the term "fracturing fluid" refers to fluids
or slurries used downhole during fracturing operations.
[0041] As used herein, the term "spotting fluid" refers to fluids
or slurries used downhole during spotting operations, and can be
any fluid designed for localized treatment of a downhole region. In
one example, a spotting fluid can include a lost circulation
material for treatment of a specific section of the wellbore, such
as to seal off fractures in the wellbore and prevent sag. In
another example, a spotting fluid can include a water control
material. In some examples, a spotting fluid can be designed to
free a stuck piece of drilling or extraction equipment, can reduce
torque and drag with drilling lubricants, prevent differential
sticking, promote wellbore stability, and can help to control mud
weight.
[0042] As used herein, the term "completion fluid" refers to fluids
or slurries used downhole during the completion phase of a well,
including cementing compositions.
[0043] As used herein, the term "remedial treatment fluid" refers
to fluids or slurries used downhole for remedial treatment of a
well, and can also be called a "work-over fluid." Remedial
treatments, also called work-over treatments, can include
treatments designed to increase or maintain the production rate of
a well, such as stimulation or clean-up treatments.
[0044] As used herein, the term "abandonment fluid" refers to
fluids or slurries used downhole during or preceding the
abandonment phase of a well.
[0045] As used herein, the term "acidizing fluid" refers to fluids
or slurries used downhole during acidizing treatments. In one
example, an acidizing fluid is used in a clean-up operation to
remove material obstructing the flow of desired material, such as
material formed during a perforation operation. In some examples,
an acidizing fluid can be used for damage removal.
[0046] As used herein, the term "cementing fluid" refers to fluids
or slurries used during cementing operations of a well. For
example, a cementing fluid can include an aqueous mixture including
at least one of cement and cement kiln dust. In another example, a
cementing fluid can include a curable resinous material such as a
polymer that is in an at least partially uncured state.
[0047] As used herein, the term "water control material" refers to
a solid or liquid material that interacts with aqueous material
downhole, such that hydrophobic material can more easily travel to
the surface and such that hydrophilic material (including water)
can less easily travel to the surface. A water control material can
be used to treat a well to cause the proportion of water produced
to decrease and to cause the proportion of hydrocarbons produced to
increase, such as by selectively binding together material between
water-producing subterranean formations and the wellbore while
still allowing hydrocarbon-producing formations to maintain
output.
[0048] As used herein, the term "packer fluid" refers to fluids or
slurries that can be placed in the annular region of a well between
tubing and outer casing above a packer. In various examples, the
packer fluid can provide hydrostatic pressure in order to lower
differential pressure across the sealing element, lower
differential pressure on the wellbore and casing to prevent
collapse, and protect metals and elastomers from corrosion.
[0049] As used herein, the term "fluid" refers to liquids and gels,
unless otherwise indicated.
[0050] As used herein, the term "subterranean material" or
"subterranean formation" refers to any material under the surface
of the earth, including under the surface of the bottom of the
ocean. For example, a subterranean formation or material can be any
section of a wellbore and any section of a subterranean petroleum-
or water-producing formation or region in fluid contact with the
wellbore. Placing a material in a subterranean formation can
include contacting the material with any section of a wellbore or
with any subterranean region in fluid contact therewith.
Subterranean materials can include any materials placed into the
wellbore such as cement, drill shafts, liners, tubing, casing, or
screens; placing a material in a subterranean formation can include
contacting with such subterranean materials. In some examples, a
subterranean formation or material can be any below-ground region
that can produce liquid or gaseous petroleum materials, water, or
any section below-ground in fluid contact therewith. For example, a
subterranean formation or material can be at least one of an area
desired to be fractured, a fracture or an area surrounding a
fracture, and a flow pathway or an area surrounding a flow pathway,
wherein a fracture or a flow pathway can be optionally fluidly
connected to a subterranean petroleum- or water-producing region,
directly or through one or more fractures or flow pathways.
[0051] As used herein, "treatment of a subterranean formation" can
include any activity directed to extraction of water or petroleum
materials from a subterranean petroleum- or water-producing
formation or region, for example, including drilling, stimulation,
hydraulic fracturing, clean-up, acidizing, completion, cementing,
remedial treatment, abandonment, and the like.
[0052] As used herein, a "flow pathway" downhole can include any
suitable subterranean flow pathway through which two subterranean
locations are in fluid connection. The flow pathway can be
sufficient for petroleum or water to flow from one subterranean
location to the wellbore or vice-versa. A flow pathway can include
at least one of a hydraulic fracture, and a fluid connection across
a screen, across gravel pack, across proppant, including across
resin-bonded proppant or proppant deposited in a fracture, and
across sand. A flow pathway can include a natural subterranean
passageway through which fluids can flow. In some embodiments, a
flow pathway can be a water source and can include water. In some
embodiments, a flow pathway can be a petroleum source and can
include petroleum. In some embodiments, a flow pathway can be
sufficient to divert from a wellbore, fracture, or flow pathway
connected thereto at least one of water, a downhole fluid, or a
produced hydrocarbon.
[0053] As used herein, a "carrier fluid" refers to any suitable
fluid for suspending, dissolving, mixing, or emulsifying with one
or more materials to form a composition. For example, the carrier
fluid can be at least one of crude oil, dipropylene glycol methyl
ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl
ether, dipropylene glycol dimethyl ether, dimethyl formamide,
diethylene glycol methyl ether, ethylene glycol butyl ether,
diethylene glycol butyl ether, butylglycidyl ether, propylene
carbonate, D-limonene, a C.sub.2-C.sub.40 fatty acid
C.sub.1-C.sub.10 alkyl ester (e.g., a fatty acid methyl ester),
tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate,
2-butoxy ethanol, butyl acetate, butyl lactate, furfuryl acetate,
dimethyl sulfoxide, dimethyl formamide, a petroleum distillation
product or fraction (e.g., diesel, kerosene, napthas, and the like)
mineral oil, a hydrocarbon oil, a hydrocarbon including an aromatic
carbon-carbon bond (e.g., benzene, toluene), a hydrocarbon
including an alpha olefin, xylenes, an ionic liquid, methyl ethyl
ketone, an ester of oxalic, maleic or succinic acid, methanol,
ethanol, propanol (iso- or normal-), butyl alcohol (iso-, tert-, or
normal-), an aliphatic hydrocarbon (e.g., cyclohexanone, hexane),
water, brine, produced water, flowback water, brackish water, and
sea water. The fluid can form about 0.001 wt % to about 99.999 wt %
of a composition including the silane-functionalized PAI clay
stabilizer, or a mixture including the same, or about 0.001 wt % or
less, 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35,
40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, 99,
99.9, 99.99, or about 99.999 wt % or more.
[0054] In various embodiments, salts having a positively charged
counterion can include any suitable positively charged counterion.
For example, the counterion can be ammonium(NH.sub.4.sup.+), or an
alkali metal such as sodium (Na.sup.+), potassium (K.sup.+), or
lithium (Li.sup.+). In some embodiments, the counterion can have a
positive charge greater than +1, which can in some embodiments
complex to multiple ionized groups, such as Zn.sup.2+, Al.sup.3+,
or alkaline earth metals such as Ca.sup.2+ or Mg.sup.2+.
[0055] In various embodiments, salts having a negatively charged
counterion can include any suitable negatively charged counterion.
For example, the counterion can be a halide, such as fluoride,
chloride, iodide, or bromide. In other examples, the counterion can
be nitrate, hydrogen sulfate, dihydrogen phosphate, bicarbonate,
nitrite, perchlorate, iodate, chlorate, bromate, chlorite,
hypochlorite, hypobromite, cyanide, amide, cyanate, hydroxide,
permanganate. The counterion can be a conjugate base of any
carboxylic acid, such as acetate or formate. In some embodiments, a
counterion can have a negative charge greater than -1, which can in
some embodiments complex to multiple ionized groups, such as oxide,
sulfide, nitride, arsenate, phosphate, arsenite, hydrogen
phosphate, sulfate, thiosulfate, sulfite, carbonate, chromate,
dichromate, peroxide, or oxalate.
[0056] The polymers described herein can independently terminate in
any suitable way. In some embodiments, the polymers can
independently terminate with an end group that is independently
chosen from a suitable polymerization initiator, --H, --OH, a
substituted or unsubstituted (C.sub.1-C.sub.20)hydrocarbyl (e.g.,
(C.sub.1-C.sub.10)alkyl or (C.sub.6-C.sub.20)aryl) interrupted with
0, 1, 2, or 3 groups independently selected from --O--, substituted
or unsubstituted --NH--, and --S--, a poly(substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbyloxy), and a
poly(substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbylamino). The polymers can independently
have the same or different terminal groups.
[0057] As used herein, a "clay stabilizer" is a material that slows
or prevents the mechanical or chemical disaggregation of clay, and
"clay stabilization" is the slowing or prevention of mechanical or
chemical disaggregation of clay. Clay stabilizer can also include
the slowing or prevention of generation of fines associated with
the clay.
[0058] In various embodiments, the present invention provides a
method of treating a subterranean formation. The method includes
placing in the subterranean formation a silane-functionalized
polyalkyleneimine (PAI) clay stabilizer.
[0059] In various embodiments, the present invention provides a
method of treating a subterranean formation. The method includes
placing in the subterranean formation a silane-functionalized
polyalkyleneimine (PAI) clay stabilizer. The silane-functionalized
PAI clay stabilizer is a polymer including a repeating unit having
the following structure:
##STR00001##
At each occurrence of R.sup.1 and D in the same repeating unit, a)
R.sup.1 is independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and D is H, or b)
R.sup.1 and D together in the same repeating unit form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.1 is bound.
At each occurrence, X is independently selected from the group
consisting of --(CH.sub.2).sub.2--O--, --(CH.sub.2).sub.3--O--,
--(CH.sub.2).sub.2--S--, --(CH.sub.2).sub.3--S--, and a
--(C.sub.1-10)alkylene-. At each occurrence, m is about 0 to about
10. At each occurrence, L.sup.1 is a substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbylene interrupted by 0, 1, 2, or 3
groups independently selected from --O--, --S--, and substituted or
unsubstituted --NH--. At each occurrence, R.sup.A is independently
selected from --O--R.sup.B, --H, and --R.sup.B, wherein at least
one R.sup.A of each --Si--(R.sup.A).sub.3 is --O--R.sup.B. At each
occurrence, R.sup.B is independently substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl. At each occurrence of R.sup.2 and E
in the same R.sup.1 or in the same R.sup.3, a) R.sup.2 is
independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHF--N(R.sup.3).sub.2, and E is H, or b)
R.sup.2 and E together in the same R.sup.1 or in the same R.sup.3
form a (C.sub.1-C.sub.10)heterocycle with the N to which R.sup.2 is
bound. At each occurrence of R.sup.3 and F in the same R.sup.2, a)
R.sup.3 is independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and F is H, or b)
R.sup.3 and F together in the same R.sup.2 form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.3 is bound.
At one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, and R.sup.3 in the silane-functionalized PAI clay
stabilizer molecule is a silicon-containing group. Each amine group
is independently in the form of a neutral amine or a protonated
cationic amine.
[0060] In various embodiments, the present invention provides a
method of treating a subterranean formation. The method includes
placing in the subterranean formation a silane-functionalized
polyethyleneimine (PEI) clay stabilizer. The silane-functionalized
PEI clay stabilizer is a polymer including a repeating unit having
the following structure:
##STR00002##
At each occurrence, R.sup.1 is independently selected from the
group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At each occurrence, L.sup.1
is a substituted or unsubstituted (C.sub.1-C.sub.20)hydrocarbylene
interrupted by 0, 1, 2, or 3 groups independently selected from
--O--, --S--, and substituted or unsubstituted --NH--. At each
occurrence, R.sup.A is independently selected from --O--R.sup.B,
--H, and --R.sup.B, wherein at least one R.sup.A of each
--Si--(R.sup.A).sub.3 is --O--R.sup.B. At each occurrence, R.sup.B
is independently substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl. At each occurrence, R.sup.2 is
independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2. At each occurrence, R.sup.3
is independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At one or more occurrences,
at least one group selected from R.sup.1, R.sup.2, and R.sup.3 in
the silane-functionalized PEI clay stabilizer molecule is a
silicon-containing group. Each amine group is independently in the
form of a neutral amine or a protonated cationic amine.
[0061] In various embodiments, the present invention provides a
system. The system includes a tubular disposed in a subterranean
formation. The system also includes a pump configured to pump a
clay stabilizer composition including a silane-functionalized PAI
clay stabilizer in the subterranean formation through the
tubular.
[0062] In various embodiments, the present invention provides a
silane-functionalized polyalkyleneimine (PAI) clay stabilizer for
treatment of a subterranean formation, wherein the
silane-functionalized PAI clay stabilizer is a polymer including a
repeating unit having the following structure:
##STR00003##
At each occurrence of R.sup.1 and D in the same repeating unit, a)
R.sup.1 is independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and D is H, or b)
R.sup.1 and D together in the same repeating unit form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.1 is bound.
At each occurrence, X is independently selected from the group
consisting of --(CH.sub.2).sub.2--O--, --(CH.sub.2).sub.3--O--,
--(CH.sub.2).sub.2--S--, --(CH.sub.2).sub.3--S--, and a
--(C.sub.1-10)alkylene-. At each occurrence, m is about 0 to about
10. At each occurrence, L.sup.1 is a substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbylene interrupted by 0, 1, 2, or 3
groups independently selected from --O--, --S--, and substituted or
unsubstituted --NH--. At each occurrence, R.sup.A is independently
selected from --O--R.sup.B, --H, and --R.sup.B, wherein at least
one R.sup.A of each --Si--(R.sup.A).sub.3 is --O--R.sup.B. At each
occurrence, R.sup.B is independently substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl. At each occurrence of R.sup.2 and E
in the same R.sup.1 or in the same R.sup.3, a) R.sup.2 is
independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHF--N(R.sup.3).sub.2, and E is H, or b)
R.sup.2 and E together in the same R.sup.1 or in the same R.sup.3
form a (C.sub.1-C.sub.10)heterocycle with the N to which R.sup.2 is
bound. At each occurrence of R.sup.3 and F in the same R.sup.2, a)
R.sup.3 is independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and F is H, or b)
R.sup.3 and F together in the same R.sup.2 form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.3 is bound.
At one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, and R.sup.3 in the silane-functionalized PAI clay
stabilizer molecule is a silicon-containing group. Each amine group
is independently in the form of a neutral amine or a protonated
cationic amine.
[0063] In various embodiments, the present invention provides a
silane-functionalized PEI clay stabilizer for treatment of a
subterranean formation. The silane-functionalized PEI clay
stabilizer is a polymer including a repeating unit having the
following structure:
##STR00004##
At each occurrence, R.sup.1 is independently selected from the
group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At each occurrence, L.sup.1
is a substituted or unsubstituted (C.sub.1-C.sub.20)hydrocarbylene
interrupted by 0, 1, 2, or 3 groups independently selected from
--O--, --S--, and substituted or unsubstituted --NH--. At each
occurrence, R.sup.A is independently selected from --O--R.sup.B,
--H, and --R.sup.B, wherein at least one R.sup.A of each
--Si--(R.sup.A).sub.3 is --O--R.sup.B. At each occurrence, R.sup.B
is independently substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl. At each occurrence, R.sup.2 is
independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2. At each occurrence, R.sup.3
is independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At one or more occurrences,
at least one group selected from R.sup.1, R.sup.2, and R.sup.3 in
the silane-functionalized clay stabilizer PEI molecule is a
silicon-containing group. Each amine group is independently in the
form of a neutral amine or a protonated cationic amine.
[0064] In various embodiments, the present invention provides a
silane-functionalized PEI clay stabilizer for treatment of a
subterranean formation, wherein the silane-functionalized PEI clay
stabilizer has the structure:
##STR00005##
At each occurrence, R.sup.1 is independently selected from the
group consisting of --H,
--CH.sub.2--CH(OH)--(C.sub.1-C.sub.8)alkylene-O--(C.sub.1-C.sub.10)alkyle-
ne-Si(O--(C.sub.1-C.sub.10)alkyl).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, wherein at each occurrence,
each (C.sub.1-C.sub.10)alkylene, (C.sub.1-C.sub.5)alkylene, and
(C.sub.1-C.sub.10)alkyl is independently selected. At each
occurrence, R.sup.2 is independently selected from the group
consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2. At each occurrence, R.sup.3
is independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At each occurrence, R.sup.4
is independently selected from the group consisting of --H and
-L.sup.1-Si--(R.sup.A).sub.3. At one or more occurrences, at least
one group selected from R.sup.1, R.sup.2, R.sup.3, and R.sup.4 in
the silane-functionalized clay stabilizer PEI molecule is a
silicon-containing group. The variable n is about 2 to about
1,000,000. Each amine group is independently in the form of a
neutral amine or a protonated cationic amine.
[0065] In various embodiments, the present invention provides a
method of preparing a silane-functionalized PAI clay stabilizer for
treatment of a subterranean formation. The method includes forming
a mixture including a silane-functionalized epoxide and a PAL. The
method also includes allowing the mixture to react to form the
silane-functionalized PAI clay stabilizer.
[0066] In various embodiments, the present invention provides
certain advantages over other clay stabilizers and methods of using
the same, at least some of which are unexpected. For example, in
some embodiments, the clay stabilizer provides clay and fines
control using both electrostatic interaction with the clay and
covalent bond formation to the clay (e.g., via formation of silyl
bonds to the clay), unlike other clay stabilizers which only
provide electrostatic interactions. By providing both electrostatic
interactions and covalent bond formations, in various embodiments,
the clay stabilizer can provide better control of clay swelling,
clay migration, fines generation (e.g., from proppant pack,
subterranean formation, or both), or a combination thereof.
[0067] In various embodiments, due to silyl bond formation to the
clay, the clay stabilizer can provide stronger binding to the clay
than provided by other clay stabilizers. In various embodiments, as
compared to other clay stabilizers, the clay stabilizer of the
present invention can provide a more long-lasting or permanent
stabilization against clay swelling, clay migration, fines
generation, or a combination thereof, in water-sensitive
formations.
[0068] In various embodiments, the clay stabilizer can provide
fracture face protection, providing a network of clay stabilization
at the fracture face, which can prevent formation softening,
prevent formation invasion into the proppant pack, prevent proppant
embedment into the formation, or a combination thereof. In various
embodiments, the clay stabilizer can be more cost effective than
other clay stabilizers, and can be formed from readily-available
and inexpensive materials. In various embodiments, the clay
stabilizer can provide a given amount of stabilization against clay
swelling, clay migration, fines generation, or a combination
thereof, for a lower cost than other clay stabilizers. In various
embodiments, the structure of the clay stabilizer can be easily
varied to give customized performance under various conditions,
such as variation of the degree of branching of the clay
stabilizer, variation of the molecular weight of the clay
stabilizer, and the degree of silyl-group functionalization of the
clay stabilizer. In various embodiments, the clay stabilizer can be
longer lasting than other clay stabilizers, and can be resistant to
being washed-off during flow back, production, acid treatments,
restimulation of the well, or a combination thereof.
Method of Treating a Subterranean Formation.
[0069] In various embodiments, the present invention provides a
method of treating a subterranean formation. The method can include
placing in the subterranean formation a silane-functionalized PAI
clay stabilizer. In some embodiments, the silane-functionalized PAI
clay stabilizer is included in a clay stabilizer composition, and
the method includes placing the clay stabilizer composition in the
subterranean formation. The method can include using the clay
stabilizer composition in the subterranean formation, at least one
of alone and in combination with other materials, as a drilling
fluid, stimulation fluid, fracturing fluid, spotting fluid,
clean-up fluid, completion fluid, remedial treatment fluid,
abandonment fluid, pill, acidizing fluid, cementing fluid, packer
fluid, logging fluid, or a combination thereof. The method can
include performing an operation in the subterranean formation such
as drilling, stimulating, fracturing, acidizing, cementing packing,
logging; performing a clean-up procedure, a completion procedure, a
remedial treatment procedure, an abandonment procedure; applying a
pill; using a packer fluid; or a combination thereof.
[0070] Clay units typically organize into face-to-face aggregates,
but in aqueous conditions, these faces can become negatively
charged as water intercalates and exfoliates the clay layers. At
the edges, the clay sheets contain an abundance of oxygen atoms and
hydroxyl groups that can accept and release protons. Proton release
is a dynamic equilibrium and therefore at any given time there is a
presence of hydroxyl groups as well as negative charge distribution
on the surface of the clay.
[0071] The silane-functionalized PAI clay stabilizer can form silyl
bonds to clay in the subterranean formation, such as via reaction
with --OH groups on the clay surface. For example, an --OH on the
clay face can react with Si--O-hydrocarbyl to form an --O--Si bond
between the clay stabilizer and the surface of the clay. The
formation of silyl bonds between the clay stabilizer and the
surface of the clay can provide long-lasting stabilization of the
clay. Alternatively, the silyl bonds can be formed between the
surface of a proppant and the clay stabilizer. The
silane-functionalized PAI clay stabilizer can also interact
electrostatically (e.g., electrostatic adsorption) with charges on
the surface of the clay. For example, ammonium groups in the clay
stabilizer can bind with negative charges on the surface of the
clay (e.g., --O-- groups, or other negatively charged groups), to
bind the clay and the clay stabilizer together. The association
between the silane-functionalized PAI clay stabilizer and the clay
can hold the clay together, preventing or reducing swelling of the
clay, preventing or reducing migration of the clay, preventing or
reducing migration of fines associated with the clay (e.g., fines
that are in the clay or near the clay), or a combination thereof,
such as compared to a corresponding composition free of the
silane-functionalized PAI clay stabilizer or having less of the
silane-functionalized PAI clay stabilizer therein.
[0072] Any suitable type of clay can be stabilized by the clay
stabilizer. For example, clays of the montmorillonite (smectite)
group such as montmorillonite, saponite, nontronite, hectorite, and
sauconite; the kaolin group such as kaolinite, nacrite, dickite,
and halloysite; the hydrousmica group such as hydrobiotite,
glauconite, illite, and bramallite; the chlorite group such as
chlorite and chamosite; clay minerals not belonging to the above
groups such as vermiculite, attapulgite, and sepiolite; and
mixed-layer varieties of the such minerals and groups. Other
mineral components may further be associated with the clay. The
clay stabilizer can be a shale stabilizer.
[0073] The placing of the silane-functionalized PAI clay stabilizer
or a clay stabilizer composition including the same in the
subterranean formation can include contacting the clay stabilizer
or the clay stabilizer composition and any suitable part of the
subterranean formation, or contacting the clay stabilizer or the
clay stabilizer composition and a subterranean material, such as
any suitable subterranean material. The subterranean formation can
be any suitable subterranean formation. In some examples, the
placing of the clay stabilizer or the clay stabilizer composition
in the subterranean formation includes contacting the clay
stabilizer or the clay stabilizer composition with or placing the
clay stabilizer or the clay stabilizer composition in at least one
of a fracture, a part of an area surrounding a fracture, a flow
pathway, an area surrounding a flow pathway, and an area desired to
be fractured. The placing of the clay stabilizer or the clay
stabilizer composition in the subterranean formation can be any
suitable placing and can include any suitable contacting between
the subterranean formation and the clay stabilizer or the clay
stabilizer composition. The placing of the clay stabilizer or the
clay stabilizer composition in the subterranean formation can
include at least partially depositing the clay stabilizer or the
clay stabilizer composition in a fracture, flow pathway, or area
surrounding the same.
[0074] In some embodiments, the method includes obtaining or
providing the clay stabilizer composition including the
silane-functionalized PAI clay stabilizer. The obtaining or
providing of the clay stabilizer composition can occur at any
suitable time and at any suitable location. The obtaining or
providing of the clay stabilizer composition can occur above the
surface (e.g., one or more components of the clay stabilizer
composition can be combined above the surface). The obtaining or
providing of the composition can occur in the subterranean
formation (e.g., one or more components of the clay stabilizer
composition can be combined downhole). The method can include
combining the silane-functionalized PAI clay stabilizer with an
aqueous or oil-based fluid including a drilling fluid, stimulation
fluid, fracturing fluid, spotting fluid, clean-up fluid, completion
fluid, remedial treatment fluid, abandonment fluid, pill, acidizing
fluid, cementing fluid, packer fluid, logging fluid, or a
combination thereof, to form the clay stabilizer composition.
[0075] The method can include hydraulic fracturing, such as a
method of hydraulic fracturing to generate a fracture or flow
pathway. The placing of the clay stabilizer or the clay stabilizer
composition in the subterranean formation or the contacting of the
subterranean formation and the hydraulic fracturing can occur at
any time with respect to one another; for example, the hydraulic
fracturing can occur at least one of before, during, and after the
contacting or placing. In some embodiments, the contacting or
placing occurs during the hydraulic fracturing, such as during any
suitable stage of the hydraulic fracturing, such as during at least
one of a pre-pad stage (e.g., during injection of water with no
proppant, and additionally optionally mid- to low-strength acid), a
pad stage (e.g., during injection of fluid only with no proppant,
with some viscosifier, such as to begin to break into an area and
initiate fractures to produce sufficient penetration and width to
allow proppant-laden later stages to enter), or a slurry stage of
the fracturing (e.g., viscous fluid with proppant). The method can
include performing a stimulation treatment at least one of before,
during, and after placing the clay stabilizer or the clay
stabilizer composition in the subterranean formation in the
fracture, flow pathway, or area surrounding the same. The
stimulation treatment can be, for example, at least one of
perforating, acidizing, injecting of cleaning fluids, propellant
stimulation, and hydraulic fracturing. In some embodiments, the
stimulation treatment at least partially generates a fracture or
flow pathway where the clay stabilizer or the clay stabilizer
composition is placed in or contacted to, or the clay stabilizer or
the clay stabilizer composition is placed in or contacted to an
area surrounding the generated fracture or flow pathway.
[0076] The clay stabilizer composition including the
silane-functionalized PAI clay stabilizer can be an oil-based
composition (e.g., 50 wt % or more oil-based liquids) or a
water-based composition (e.g., 50 wt % or more water). The clay
stabilizer composition can be a water- or oil-based emulsion,
wherein the silane-functionalized PAI can be at least partially
dissolved in the water-phase of the emulsion.
[0077] The clay stabilizer composition can include a carrier fluid.
The PAI clay stabilizer can be dispersed, dissolved, or a
combination thereof, in the carrier fluid. The carrier fluid can
include any one or more suitable fluids. The carrier fluid (e.g.,
the one or more fluids) can form any suitable proportion of the
clay stabilizer composition, such as about 0.001 wt % to about
99.999 wt % of the clay stabilizer composition, about 50 wt % to
about 99.999 wt %, about 80 wt % to about 99.999 wt %, or about
0.001 wt % or less, or about less than, equal to, or more than
about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20,
25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 72, 74, 76, 78, 80, 82, 84,
86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99 wt %,
or about 99.999 wt % or more.
[0078] The clay stabilizer composition can include one
silane-functionalized PAI clay stabilizer, or more than one
silane-functionalized PAI clay stabilizer. The one or more
silane-functionalized PAI clay stabilizers can form any suitable
proportion of the clay stabilizer composition, such as about 0.0001
wt % to about 99.999 wt % of the clay stabilizer composition, or
about 0.001 wt % to about 10 wt %, about 0.0001 wt % or less, or
less than, equal to, or more than about 0.001 wt %, 0.01, 0.1, 1,
2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20,
25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90,
91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99 wt %, or about
99.999 wt % or more.
Silane-Functionalized Polyalkyleneamine (PAI) Clay Stabilizer.
[0079] In some embodiments, the silane-functionalized PAI clay
stabilizer can be a polymer (e.g., a homopolymer or a copolymer)
including a repeating unit having the following structure:
##STR00006##
At each occurrence of R.sup.1 and D in the same repeating unit, a)
R.sup.1 can be independently selected from the group consisting of
--H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and D is H, or b)
R.sup.1 and D together in the same repeating unit can form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.1 is bound.
At each occurrence, X can be independently selected from the group
consisting of --(CH.sub.2).sub.2--O--, --(CH.sub.2).sub.3--O--,
--(CH.sub.2).sub.2--S--, --(CH.sub.2).sub.3--S--, and a
--(C.sub.1-10)alkylene-. At each occurrence, m can be about 0 to
about 10 (e.g., 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10). At each
occurrence, L.sup.1 can be a substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbylene interrupted by 0, 1, 2, or 3
groups independently selected from --O--, --S--, and substituted or
unsubstituted --NH--. At each occurrence, R.sup.A can be
independently selected from --O--R.sup.B, --H, and --R.sup.B,
wherein at least one R.sup.A of each --Si--(R.sup.A).sub.3 is
--O--R.sup.B. At each occurrence, R.sup.B can be independently
substituted or unsubstituted (C.sub.1-C.sub.20)hydrocarbyl. At each
occurrence of R.sup.2 and E in the same R.sup.1 or in the same
R.sup.3, a) R.sup.2 can be independently selected from the group
consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHF--N(R.sup.3).sub.2, and E is H, or b)
R.sup.2 and E together in the same R.sup.1 or in the same R.sup.3
can form a (C.sub.1-C.sub.10)heterocycle with the N to which
R.sup.2 is bound. At each occurrence of R.sup.3 and F in the same
R.sup.2, a) R.sup.3 is independently selected from the group
consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and F is H, or b)
R.sup.3 and F together in the same R.sup.2 form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.3 is bound.
At one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, and R.sup.3 in the silane-functionalized PAI clay
stabilizer molecule is a silicon-containing group. Each amine group
can be independently in the form of a neutral amine or a protonated
cationic amine.
[0080] The silane-functionalized PAI clay stabilizer can have the
structure:
##STR00007##
At each occurrence of R.sup.4 in an end group not including G,
R.sup.4 can be independently selected from the group consisting of
--H and -L.sup.1-Si--(R.sup.A).sub.3. At each occurrence of R.sup.4
and G in the same end group, a) R.sup.4 can be independently
selected from the group consisting of --H and
-L.sup.1-Si--(R.sup.A).sub.3 and G is H, or b) R.sup.4 and G
together in the same end group can form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.4 is bound.
The variable n can be about 2 to about 1,000,000. Each amine group
can be independently in the form of a neutral amine or a protonated
cationic amine.
[0081] In some embodiments, the silane-functionalized PAI clay
stabilizer can be a polyethyleneimine (PEI) clay stabilizer. At
each occurrence m can be 0. At each occurrence D, E, F, and G can
be H. The silane-functionalized PEI clay stabilizer can be a
polymer (e.g., a homopolymer or a copolymer) including a repeating
unit having the following structure:
##STR00008##
Each amine group can be independently in the form of a neutral
amine or a protonated cationic amine. At each occurrence, R.sup.2
can be independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2. At each occurrence, R.sup.3
can be independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At one or more occurrences,
at least one group selected from R.sup.1, R.sup.2, and R.sup.3 in
the silane-functionalized PEI clay stabilizer molecule can be a
silicon-containing group
[0082] At each occurrence, R.sup.1 can be independently selected
from the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At each occurrence, L.sup.1
can be a substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbylene interrupted by 0, 1, 2, or 3
groups independently selected from --O--, --S--, and substituted or
unsubstituted --NH--. At each occurrence, L.sup.1 can be a
substituted or unsubstituted (C.sub.1-C.sub.20)alkylene interrupted
by --O--. At each occurrence, L.sup.1 independently can have the
structure -L.sup.2-O-L.sup.3-. At each occurrence, L.sup.2 can be
independently substituted or unsubstituted
(C.sub.1-C.sub.10)alkylene. At each occurrence, L.sup.2 can be
independently unsubstituted (C.sub.1-C.sub.5)alkylene. At each
occurrence, L.sup.3 can be independently substituted or
unsubstituted (C.sub.1-C.sub.10)alkylene. At each occurrence,
L.sup.3 can be independently a hydroxy-substituted
(C.sub.1-C.sub.10)alkylene. At each occurrence, L.sup.3 can be
independently --(C.sub.1-C.sub.8)alkylene-CH(OH)--CH.sub.2--,
wherein the hydroxy group is on the carbon beta to the amine. The
variable L.sup.3 can be --CH.sub.2--CH(OH)--CH.sub.2--. The
variable L.sup.1 can be
--(CH.sub.2).sub.3--O--CH.sub.2--CH(OH)--CH.sub.2--, wherein the
hydroxy group is on the carbon beta to the amine. At each
occurrence, R.sup.A can be independently selected from
--O--R.sup.B, --H, and --R.sup.B, wherein at least one R.sup.A of
each --Si--(R.sup.A).sub.3 is --O--R.sup.B. At each occurrence,
R.sup.B can be independently substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl. The variable R.sup.A can be
--O--R.sup.B. At each occurrence, R.sup.B can be independently
(C.sub.1-C.sub.20)alkyl. At each occurrence, R.sup.B can be
independently (C.sub.1-C.sub.5)alkyl. The variable R.sup.B can be
methyl. The group -L.sup.1-Si--(R.sup.A).sub.3 can be
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).sub.3.
[0083] The silane-functionalized PAI clay stabilizer can be a
homopolymer. The silane-functionalized PAI clay stabilizer can have
the structure:
##STR00009##
Each amine group is independently in the form of a neutral amine or
a protonated cationic amine. At each occurrence, R.sup.4 can be
independently selected from the group consisting of --H and
-L.sup.1-Si--(R.sup.A).sub.3. The variable n is about 2 to about
1,000,000, about 2 to about 1,000, about 2 to about 100, or about
2, or less than, equal to, or greater than 3, 4, 5, 6, 7, 8, 9, 10,
12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 35, 40, 45, 50, 55, 60, 65,
70, 75, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350, 400, 450,
500, 600, 700, 800, 900, 1,000, 1,500, 2,000, 2,500, 5,000, 10,000,
20,000, 50,000, 100,000, 500,000, or about 1,000,000 or more. At
one or more occurrences, at least one group selected from R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 in the silane-functionalized PEI clay
stabilizer molecule is a silicon-containing group.
[0084] The ratio of the number of -L.sup.1-Si--(R.sup.A).sub.3
groups in the silane-functionalized PAI to the number of times the
repeating group repeats can be any suitable ratio, such as about
1:100,000 to about 100:1, about 2:1 to about 6:1, about 1:100,000
or less, or less than, equal to, or more than about 1:50,000,
1:10,000, 1:5,000, 1:2,500, 1:1,000, 1:500, 1:250, 1:100, 1:50,
1:25, 1:10, 1:8, 1:6, 1:4, 1:2, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1,
4:1, 4.5:1, 5:1, 5.5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 12:1, 14:1, 16:1,
20:1, 25:1, 50:1, 75:1, or about 100:1 or more. In various
embodiments, each PAI repeating unit includes at least 2 silane
groups, or 3, 4, 5, or at least 6 or more silane groups. The ratio
of the number of quaternary ammonium groups (e.g.,
--NH.sub.3.sup.+, --NRH.sub.2.sup.+, --NR.sub.2H.sup.+, or a
combination thereof), or of the number of primary and secondary
amine groups (e.g., protonated or not protonated), to the number of
times the repeating group repeats can be any suitable ratio, such
as about 1:100,000 to about 100:1, about 2:1 to about 6:1, about
1:100,000 or less, or less than, equal to, or more than about
1:50,000, 1:10,000, 1:5,000, 1:2,500, 1:1,000, 1:500, 1:250, 1:100,
1:50, 1:25, 1:10, 1:8, 1:6, 1:4, 1:2, 1:1, 1.5:1, 2:1, 2.5:1, 3:1,
3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 12:1,
14:1, 16:1, 20:1, 25:1, 50:1, 75:1, or about 100:1 or more. Per
molecule, the clay stabilizer can include any suitable number of
primary and secondary amine groups, e.g., --NH.sub.2,
--NH.sub.3.sup.+, --NRH.sub.2.sup.+, --NR.sub.2H.sup.+, or a
combination thereof, such as greater than, equal to, or less than,
about 1,000,000, 500,000, 100,000, 50,000, 20,000, 10,000, 5,000,
2,000, 1,000, 500, 250, 100, 50, 25, 10, 8, 6, 4, 2, or 1.
[0085] The silane-functionalized PEI clay stabilizer can have the
structure:
##STR00010##
Each amine group is independently in the form of a neutral amine or
a protonated cationic amine. At each occurrence, R.sup.1 can be
independently selected from the group consisting of --H,
--CH.sub.2--CH(OH)--(C.sub.1-C.sub.8)alkylene-O--(C.sub.1-C.sub.10)alkyle-
ne-Si(O--(C.sub.1-C.sub.10)alkyl).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, wherein at each occurrence,
each (C.sub.1-C.sub.10)alkylene, (C.sub.1-C.sub.8)alkylene, and
(C.sub.1-C.sub.10)alkyl is independently selected. At each
occurrence, R.sup.2 can be independently selected from the group
consisting of --H,
--CH.sub.2--CH(OH)--(C.sub.1-C.sub.5)alkylene-O--(C.sub.1-C.sub.10)alkyle-
ne-Si(O--(C.sub.1-C.sub.10)alkyl).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2. At each occurrence, R.sup.3
can be independently selected from the group consisting of --H,
--CH.sub.2--CH(OH)--(C.sub.1-C.sub.5)alkylene-O--(C.sub.1-C.sub.10)alkyle-
ne-Si(O--(C.sub.1-C.sub.10)alkyl).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At each occurrence, R.sup.4
can be independently selected from the group consisting of --H and
--CH.sub.2--CH(OH)--(C.sub.1-C.sub.5)alkylene-O--(C.sub.1-C.sub.10)alkyle-
ne-Si(O--(C.sub.1-C.sub.10)alkyl).sub.3. The variable n is about 2
to about 1,000,000, about 2 to about 1,000, about 2 to about 100,
or about 2, or less than, equal to, or greater than 3, 4, 5, 6, 7,
8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 35, 40, 45, 50,
55, 60, 65, 70, 75, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350,
400, 450, 500, 600, 700, 800, 900, 1,000, 1,500, 2,000, 2,500,
5,000, 10,000, 20,000, 50,000, 100,000, 500,000, or about 1,000,000
or more.
[0086] The silane-functionalized PEI clay stabilizer can have the
structure:
##STR00011##
Each amine group is independently in the form of a neutral amine or
a protonated cationic amine. At each occurrence, R.sup.1 can be
independently selected from the group consisting of --H,
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).sub.3,
and --CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At each occurrence,
R.sup.2 can be independently selected from the group consisting of
--H,
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).sub.3,
and --CH.sub.2--CH.sub.2--N(R.sup.3).sub.2. At each occurrence,
R.sup.3 can be independently selected from the group consisting of
--H,
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).sub.3,
and --CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At each occurrence,
R.sup.4 can be independently selected from the group consisting of
--H and
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).sub.3.
At one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 in the silane-functionalized
PEI clay stabilizer molecule is a silicon-containing group. The
variable n is about 2 to about 1,000,000, about 2 to about 1,000,
about 2 to about 100, or about 2, or less than, equal to, or
greater than 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24,
26, 28, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 90, 100, 125,
150, 175, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900,
1,000, 1,500, 2,000, 2,500, 5,000, 10,000, 20,000, 50,000, 100,000,
500,000, or about 1,000,000 or more.
Other Components.
[0087] The clay stabilizer composition including the
silane-functionalized PAI clay stabilizer, or a mixture including
the composition, can include any suitable additional component in
any suitable proportion, such that the silane-functionalized PAI
clay stabilizer, clay stabilizer composition, or mixture including
the same, can be used as described herein. Any component listed in
this section can be present or not present in the composition or a
mixture including the same.
[0088] In various embodiments, the clay stabilizer composition can
further include a secondary clay stabilizer (e.g., a clay
stabilizer in addition to the silane-functionalized PAI clay
stabilizer). The secondary clay stabilizer can be potassium
chloride, a non-polymeric ionic liquid (e.g., including a
substituted imidazolium ion or a substituted quaternary ammonium
ion, such as 1-ethyl-3-methylimidazolium chloride,
tris-(2-hydroxyethyl)-methylammonium methylsulfate, methyl
tri-n-butyl ammonium methylsulfate, 1-ethyl-3-methylimidazolium
methanesulfonate, 1-butyl-3-methylimidazolium chloride,
1-butyl-3-methylimidazolium methanesulfonate,
1-ethyl-2,3-di-methylimidazolium ethylsulfate, or
1,2,3-trimethyl-imidazolium methylsulfate), an inorganic phosphate,
a polyalkoxy diamine or a salt thereof, choline or a choline
derivative, an oligomethylene diamine or a salt thereof, an
addition product of carboxymethyl cellulose and an organic amine,
1,2-cyclohexanediamine or a salt thereof, a salt of a phosphoric
acid ester of an oxyalkylated polyol, a combination of a partially
hydrolyzed acrylic copolymer potassium chloride and polyanionic
cellulose, a quaternary ammonium compound, a polymer based on
dialkyl aminoalkyl methacrylate, an aqueous solution containing a
polymer with hydrophilic and hydrophobic groups, a reaction product
of a polyhydroxyalkane and an alkylene oxide, or a combination
thereof. The secondary clay stabilizer can be CLAY GRABBER.RTM.,
CLAYSEAL.RTM., CRYSTAL-DRIL.RTM., CLAY SYNC.TM. II, Sandwedge.RTM.,
H2Zero.TM., Clayfix.TM. 3, Cla-Sta.RTM. XP, Cla-Sta.COPYRGT. FS,
Cla-Web.TM., or a combination thereof. In some embodiments, the
secondary clay stabilizer can be about 0.000.1 wt % to about 50 wt
% of the clay stabilizer composition or a mixture including the
same, about 0.000.1 wt % to about 10 wt %, about 0.004 wt % to
about 0.01 wt % of the composition, or about 0.000.1 wt % or less,
or less than, equal to, or more than about 0.000.5 wt %, 0.001,
0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10
wt % or more.
[0089] In some embodiments, the clay stabilizer composition or a
mixture including the same includes one or more viscosifiers. The
viscosifier can be any suitable viscosifier. The viscosifier can
affect the viscosity of the clay stabilizer composition or a
solvent that contacts the clay stabilizer composition at any
suitable time and location. In some embodiments, the viscosifier
provides an increased viscosity at least one of before injection
into the subterranean formation, at the time of injection into the
subterranean formation, during travel through a tubular disposed in
a borehole, once the clay stabilizer composition reaches a
particular subterranean location, or some period of time after the
clay stabilizer composition reaches a particular subterranean
location. In some embodiments, the viscosifier can be about 0.000.1
wt % to about 10 wt % of the clay stabilizer composition or a
mixture including the same, about 0.004 wt % to about 0.01 wt %, or
about 0.000.1 wt % or less, 0.000.5 wt %, 0.001, 0.005, 0.01, 0.05,
0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10 wt % or more of
the clay stabilizer composition or a mixture including the
same.
[0090] The viscosifier can include at least one of a substituted or
unsubstituted polysaccharide, and a substituted or unsubstituted
polyalkene (e.g., a polyethylene, wherein the ethylene unit is
substituted or unsubstituted, derived from the corresponding
substituted or unsubstituted ethene), wherein the polysaccharide or
polyalkene is crosslinked or uncrosslinked. The viscosifier can
include a polymer including at least one repeating unit derived
from a monomer selected from the group consisting of ethylene
glycol, acrylamide, vinyl acetate, 2-acrylamidomethylpropane
sulfonic acid or its salts, trimethylammoniumethyl acrylate halide,
and trimethylammoniumethyl methacrylate halide. The viscosifier can
include a crosslinked gel or a crosslinkable gel. The viscosifier
can include at least one of a linear polysaccharide and a
poly((C.sub.2-C.sub.10)alkene), wherein the
(C.sub.2-C.sub.10)alkene is substituted or unsubstituted. The
viscosifier can include at least one of poly(acrylic acid) or
(C.sub.1-C.sub.5)alkyl esters thereof, poly(methacrylic acid) or
(C.sub.1-C.sub.5)alkyl esters thereof, poly(vinyl acetate),
poly(vinyl alcohol), poly(ethylene glycol), poly(vinyl
pyrrolidone), polyacrylamide, poly (hydroxyethyl methacrylate),
alginate, chitosan, curdlan, dextran, derivatized dextran, emulsan,
a galactoglucopolysaccharide, gellan, glucuronan,
N-acetyl-glucosamine, N-acetyl-heparosan, hyaluronic acid, kefiran,
lentinan, levan, mauran, pullulan, scleroglucan, schizophyllan,
stewartan, succinoglycan, xanthan, diutan, welan, starch,
derivatized starch, tamarind, tragacanth, guar gum, derivatized
guar gum (e.g., hydroxypropyl guar, carboxy methyl guar, or
carboxymethyl hydroxypropyl guar), gum ghatti, gum arabic, locust
bean gum, karaya gum, cellulose, and derivatized cellulose (e.g.,
carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl
hydroxyethyl cellulose, hydroxypropyl cellulose, or methyl hydroxy
ethyl cellulose).
[0091] In some embodiments, the viscosifier can include at least
one of a poly(vinyl alcohol) homopolymer, poly(vinyl alcohol)
copolymer, a crosslinked poly(vinyl alcohol) homopolymer, and a
crosslinked poly(vinyl alcohol) copolymer. The viscosifier can
include a poly(vinyl alcohol) copolymer or a crosslinked poly(vinyl
alcohol) copolymer including at least one of a graft, linear,
branched, block, and random copolymer of vinyl alcohol and at least
one of a substituted or unsubstituted (C.sub.2-C.sub.50)hydrocarbyl
having at least one aliphatic unsaturated C--C bond therein, and a
substituted or unsubstituted (C.sub.2-C.sub.50)alkene. The
viscosifier can include a poly(vinyl alcohol) copolymer or a
crosslinked poly(vinyl alcohol) copolymer including at least one of
a graft, linear, branched, block, and random copolymer of vinyl
alcohol and at least one of vinyl phosphonic acid, vinylidene
diphosphonic acid, substituted or unsubstituted
2-acrylamido-2-methylpropanesulfonic acid, a substituted or
unsubstituted (C.sub.1-C.sub.20)alkenoic acid, propenoic acid,
butenoic acid, pentenoic acid, hexenoic acid, octenoic acid,
nonenoic acid, decenoic acid, acrylic acid, methacrylic acid,
hydroxypropyl acrylic acid, acrylamide, fumaric acid, methacrylic
acid, hydroxypropyl acrylic acid, vinyl phosphonic acid, vinylidene
diphosphonic acid, itaconic acid, crotonic acid, mesoconic acid,
citraconic acid, styrene sulfonic acid, allyl sulfonic acid,
methallyl sulfonic acid, vinyl sulfonic acid, and a substituted or
unsubstituted (C.sub.1-C.sub.20)alkyl ester thereof. The
viscosifier can include a poly(vinyl alcohol) copolymer or a
crosslinked poly(vinyl alcohol) copolymer including at least one of
a graft, linear, branched, block, and random copolymer of vinyl
alcohol and at least one of vinyl acetate, vinyl propanoate, vinyl
butanoate, vinyl pentanoate, vinyl hexanoate, vinyl 2-methyl
butanoate, vinyl 3-ethylpentanoate, vinyl 3-ethylhexanoate, maleic
anhydride, a substituted or unsubstituted
(C.sub.1-C.sub.20)alkenoic substituted or unsubstituted
(C.sub.1-C.sub.20)alkanoic anhydride, a substituted or
unsubstituted (C.sub.1-C.sub.20)alkenoic substituted or
unsubstituted (C.sub.1-C.sub.20)alkenoic anhydride, propenoic acid
anhydride, butenoic acid anhydride, pentenoic acid anhydride,
hexenoic acid anhydride, octenoic acid anhydride, nonenoic acid
anhydride, decenoic acid anhydride, acrylic acid anhydride, fumaric
acid anhydride, methacrylic acid anhydride, hydroxypropyl acrylic
acid anhydride, vinyl phosphonic acid anhydride, vinylidene
diphosphonic acid anhydride, itaconic acid anhydride, crotonic acid
anhydride, mesoconic acid anhydride, citraconic acid anhydride,
styrene sulfonic acid anhydride, allyl sulfonic acid anhydride,
methallyl sulfonic acid anhydride, vinyl sulfonic acid anhydride,
and an N--(C.sub.1-C.sub.10)alkenyl nitrogen-containing substituted
or unsubstituted (C.sub.1-C.sub.10)heterocycle. The viscosifier can
include a poly(vinyl alcohol) copolymer or a crosslinked poly(vinyl
alcohol) copolymer including at least one of a graft, linear,
branched, block, and random copolymer that includes a
poly(vinylalcohol/acrylamide) copolymer, a
poly(vinylalcohol/2-acrylamido-2-methylpropanesulfonic acid)
copolymer, a poly (acrylamide/2-acrylamido-2-methylpropanesulfonic
acid) copolymer, or a poly(vinylalcohol/N-vinylpyrrolidone)
copolymer. The viscosifier can include a crosslinked poly(vinyl
alcohol) homopolymer or copolymer including a crosslinker including
at least one of chromium, aluminum, antimony, zirconium, titanium,
calcium, boron, iron, silicon, copper, zinc, magnesium, and an ion
thereof. The viscosifier can include a crosslinked poly(vinyl
alcohol) homopolymer or copolymer including a crosslinker including
at least one of an aldehyde, an aldehyde-forming compound, a
carboxylic acid or an ester thereof, a sulfonic acid or an ester
thereof, a phosphonic acid or an ester thereof, an acid anhydride,
and an epihalohydrin.
[0092] In various embodiments, the clay stabilizer composition or a
mixture including the same can include one or more crosslinkers.
The crosslinker can be any suitable crosslinker. In some examples,
the crosslinker can be incorporated in a crosslinked viscosifier,
and in other examples, the crosslinker can crosslink a
crosslinkable material (e.g., downhole). The crosslinker can
include at least one of chromium, aluminum, antimony, zirconium,
titanium, calcium, boron, iron, silicon, copper, zinc, magnesium,
and an ion thereof. The crosslinker can include at least one of
boric acid, borax, a borate, a (C.sub.1-C.sub.30)hydrocarbylboronic
acid, a (C.sub.1-C.sub.30)hydrocarbyl ester of a
(C.sub.1-C.sub.30)hydrocarbylboronic acid, a
(C.sub.1-C.sub.30)hydrocarbylboronic acid-modified polyacrylamide,
ferric chloride, disodium octaborate tetrahydrate, sodium
metaborate, sodium diborate, sodium tetraborate, disodium
tetraborate, a pentaborate, ulexite, colemanite, magnesium oxide,
zirconium lactate, zirconium triethanol amine, zirconium lactate
triethanolamine, zirconium carbonate, zirconium acetylacetonate,
zirconium malate, zirconium citrate, zirconium diisopropylamine
lactate, zirconium glycolate, zirconium triethanol amine glycolate,
zirconium lactate glycolate, titanium lactate, titanium malate,
titanium citrate, titanium ammonium lactate, titanium
triethanolamine, titanium acetylacetonate, aluminum lactate, and
aluminum citrate. In some embodiments, the crosslinker can be a
(C.sub.1-C.sub.20)alkylenebiacrylamide (e.g.,
methylenebisacrylamide), a
poly((C.sub.1-C.sub.20)alkenyl)-substituted mono- or
poly-(C.sub.1-C.sub.20)alkyl ether (e.g., pentaerythritol allyl
ether), and a poly(C.sub.2-C.sub.20)alkenylbenzene (e.g.,
divinylbenzene). In some embodiments, the crosslinker can be at
least one of alkyl diacrylate, ethylene glycol diacrylate, ethylene
glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene
glycol dimethacrylate, ethoxylated bisphenol A diacrylate,
ethoxylated bisphenol A dimethacrylate, ethoxylated trimethylol
propane triacrylate, ethoxylated trimethylol propane
trimethacrylate, ethoxylated glyceryl triacrylate, ethoxylated
glyceryl trimethacrylate, ethoxylated pentaerythritol
tetraacrylate, ethoxylated pentaerythritol tetramethacrylate,
ethoxylated dipentaerythritol hexaacrylate, polyglyceryl
monoethylene oxide polyacrylate, polyglyceryl polyethylene glycol
polyacrylate, dipentaerythritol hexaacrylate, dipentaerythritol
hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol
dimethacrylate, pentaerythritol triacrylate, pentaerythritol
trimethacrylate, trimethylol propane triacrylate, trimethylol
propane trimethacrylate, tricyclodecane dimethanol diacrylate,
tricyclodecane dimethanol dimethacrylate, 1,6-hexanediol
diacrylate, and 1,6-hexanediol dimethacrylate. The crosslinker can
be about 0.000.01 wt % to about 5 wt % of the clay stabilizer
composition or a mixture including the same, about 0.001 wt % to
about 0.01 wt %, or about 0.000.01 wt % or less, or about 0.000.05
wt %, 0.000,1, 0.000,5, 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2,
3, 4, or about 5 wt % or more.
[0093] In some embodiments, the clay stabilizer composition or a
mixture including the same can include one or more breakers. The
breaker can be any suitable breaker, such that the surrounding
fluid (e.g., a fracturing fluid) can be at least partially broken
for more complete and more efficient recovery thereof, such as at
the conclusion of the hydraulic fracturing treatment. In some
embodiments, the breaker can be encapsulated or otherwise
formulated to give a delayed-release or a time-release of the
breaker, such that the surrounding liquid can remain viscous for a
suitable amount of time prior to breaking. The breaker can be any
suitable breaker; for example, the breaker can be a compound that
includes at least one of a Na.sup.+, K.sup.+, Li.sup.+, Zn.sup.+,
NH.sub.4.sup.+, Fe.sup.2+, Fe.sup.3+, Cu.sup.1+, Cu.sup.2+,
Ca.sup.2+, Mg.sup.2+, Zn.sup.2+, and an Al.sup.3' salt of a
chloride, fluoride, bromide, phosphate, or sulfate ion. In some
examples, the breaker can be an oxidative breaker or an enzymatic
breaker. An oxidative breaker can be at least one of a Na.sup.+,
K.sup.+, Li.sup.+, Zn.sup.+, NH.sub.4.sup.+, Fe.sup.2+, Fe.sup.3+,
Cu.sup.1+, Cu.sup.2+, Ca.sup.2+, Mg.sup.2+, Zn.sup.2+, and an
Al.sup.3+ salt of a persulfate, percarbonate, perborate, peroxide,
perphosphosphate, permanganate, chlorite, or hypochlorite ion. An
enzymatic breaker can be at least one of an alpha or beta amylase,
amyloglucosidase, oligoglucosidase, invertase, maltase, cellulase,
hemi-cellulase, and mannanohydrolase. The breaker can be about
0.001 wt % to about 30 wt % of the clay stabilizer composition or a
mixture including the same, or about 0.01 wt % to about 5 wt %, or
about 0.001 wt % or less, or about 0.005 wt %, 0.01, 0.05, 0.1,
0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28,
or about 30 wt % or more.
[0094] The clay stabilizer composition, or a mixture including the
clay stabilizer composition, can include any suitable fluid. For
example, the fluid can be at least one of crude oil, dipropylene
glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene
glycol methyl ether, dipropylene glycol dimethyl ether, dimethyl
formamide, diethylene glycol methyl ether, ethylene glycol butyl
ether, diethylene glycol butyl ether, butylglycidyl ether,
propylene carbonate, D-limonene, a C.sub.2-C.sub.40 fatty acid
C.sub.1-C.sub.10 alkyl ester (e.g., a fatty acid methyl ester),
tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate,
2-butoxy ethanol, butyl acetate, butyl lactate, furfuryl acetate,
dimethyl sulfoxide, dimethyl formamide, a petroleum distillation
product of fraction (e.g., diesel, kerosene, napthas, and the like)
mineral oil, a hydrocarbon oil, a hydrocarbon including an aromatic
carbon-carbon bond (e.g., benzene, toluene), a hydrocarbon
including an alpha olefin, xylenes, an ionic liquid, methyl ethyl
ketone, an ester of oxalic, maleic or succinic acid, methanol,
ethanol, propanol (iso- or normal-), butyl alcohol (iso-, tert-, or
normal-), an aliphatic hydrocarbon (e.g., cyclohexanone, hexane),
water, brine, produced water, flowback water, brackish water, and
sea water. The fluid can form about 0.001 wt % to about 99.999 wt %
of the clay stabilizer composition, or a mixture including the
same, or about 0.001 wt % or less, 0.01 wt %, 0.1, 1, 2, 3, 4, 5,
6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,
85, 90, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt % or
more.
[0095] The clay stabilizer composition including the
silane-functionalized PAI clay stabilizer or a mixture including
the same can include any suitable downhole fluid. The clay
stabilizer composition can be combined with any suitable downhole
fluid before, during, or after the placement of the composition in
the subterranean formation or the contacting of the composition and
the subterranean material. In some examples, the clay stabilizer
composition is combined with a downhole fluid above the surface,
and then the combined composition is placed in a subterranean
formation or contacted with a subterranean material. In another
example, the clay stabilizer composition is injected into a
subterranean formation to combine with a downhole fluid, and the
combined composition is contacted with a subterranean material or
is considered to be placed in the subterranean formation. The
placement of the clay stabilizer composition in the subterranean
formation can include contacting the subterranean material and the
mixture. Any suitable weight percent of the clay stabilizer
composition or of a mixture including the same that is placed in
the subterranean formation or contacted with the subterranean
material can be the downhole fluid, such as about 0.001 wt % to
about 99.999 wt %, about 0.01 wt % to about 99.99 wt %, about 0.1
wt % to about 99.9 wt %, about 20 wt % to about 90 wt %, or about
0.001 wt % or less, or about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 10, 15,
20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98,
99, 99.9, 99.99 wt %, or about 99.999 wt % or more of the clay
stabilizer composition or mixture including the same.
[0096] In some embodiments, the clay stabilizer composition, or a
mixture including the same, can include any suitable amount of any
suitable material used in a downhole fluid. For example, the clay
stabilizer composition or a mixture including the same can include
water, saline, aqueous base, acid, oil, organic solvent, synthetic
fluid oil phase, aqueous solution, alcohol or polyol, cellulose,
starch, alkalinity control agents, acidity control agents, density
control agents, density modifiers, emulsifiers, dispersants,
polymeric stabilizers, polyacrylamide, a polymer or combination of
polymers, antioxidants, heat stabilizers, foam control agents,
solvents, diluents, plasticizer, filler or inorganic particle,
pigment, dye, precipitating agent, oil-wetting agents, set
retarding additives, surfactants, gases, weight reducing additives,
heavy-weight additives, lost circulation materials, filtration
control additives, salts (e.g., any suitable salt, such as
potassium salts such as potassium chloride, potassium bromide,
potassium formate; calcium salts such as calcium chloride, calcium
bromide, calcium formate; cesium salts such as cesium chloride,
cesium bromide, cesium formate, or a combination thereof), fibers,
thixotropic additives, breakers, crosslinkers, rheology modifiers,
curing accelerators, curing retarders, pH modifiers, chelating
agents, scale inhibitors, enzymes, resins, water control materials,
oxidizers, markers, Portland cement, pozzolana cement, gypsum
cement, high alumina content cement, slag cement, silica cement,
fly ash, metakaolin, shale, zeolite, a crystalline silica compound,
amorphous silica, hydratable clays, microspheres, lime, or a
combination thereof. In various embodiments, the clay stabilizer
composition or a mixture including the same can include one or more
additive components such as: COLDTROL.RTM., ATC.RTM., OMC 2.TM.,
and OMC 42.TM. thinner additives; RHEMOD.TM. viscosifier and
suspension agent; TEMPERUS.TM. and VIS-PLUS.RTM. additives for
providing temporary increased viscosity; TAU-MOD.TM.
viscosifying/suspension agent; ADAPTA.RTM., DURATONE.RTM. HT,
THERMO TONE.TM., BDF.TM.-366, and BDF.TM.-454 filtration control
agents; LIQUITONE.TM. polymeric filtration agent and viscosifier;
FACTANT.TM. emulsion stabilizer; LE SUPERMUL.TM., EZ MUL.RTM. NT,
and FORTI-MUL.RTM.emulsifiers; DRIL TREAT.RTM. oil wetting agent
for heavy fluids; AQUATONE-S.TM. wetting agent; BARACARB.RTM.
bridging agent; BAROID.RTM. weighting agent; BAROLIFT.RTM. hole
sweeping agent; SWEEP-WATE.RTM. sweep weighting agent; BDF-508
rheology modifier; and GELTONE.RTM. II organophilic clay. In
various embodiments, the clay stabilizer composition or a mixture
including the same can include one or more additive components such
as: X-TEND.RTM. II, PAC.TM.-R, PAC.TM.-L, LIQUI-VIS.RTM. EP,
BRINEDRIL-VIS.TM., BARAZAN.RTM., N-VIS.RTM., and AQUAGEL.RTM.
viscosifiers; THERMA-CHEK.RTM., N-DRIL.TM., N-DRIL.TM. HT PLUS,
IMPERMEX.RTM., FILTERCHEK.TM., DEXTRID.RTM., CARBONOX.RTM., and
BARANEX.RTM. filtration control agents; PERFORMATROL.RTM., GEM.TM.,
EZ-MUD.RTM., CLAY GRABBER.RTM., CLAYSEAL.RTM., CRYSTAL-DRIL.RTM.,
and CLAY SYNC.TM. II shale stabilizers; NXS-LUBE.TM., EP
MUDLUBE.RTM., and DRIL-N-SLIDE.TM. lubricants; QUIK-THIN.RTM.,
IRON-THIN.TM., THERMA-THIN.COPYRGT., and ENVIRO-THIN.TM. thinners;
SOURSCAV.TM. scavenger; BARACOR.RTM. corrosion inhibitor; and
WALL-NUT.RTM., SWEEP-WATE.RTM., STOPPIT.TM., PLUG-GIT.RTM.,
BARACARB.RTM., DUO-SQUEEZE.RTM., BAROFIBRE.TM., STEELSEAL.RTM., and
HYDRO-PLUG.RTM. lost circulation management materials. Any suitable
proportion of the clay stabilizer composition or mixture including
the clay stabilizer composition can include any optional component
listed in this paragraph, such as about 0.001 wt % to about 99.999
wt %, about 0.01 wt % to about 99.99 wt %, about 0.1 wt % to about
99.9 wt %, about 20 to about 90 wt %, or about 0.001 wt % or less,
or about 0.01 wt %, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60,
70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99 wt
%, or about 99.999 wt % or more of the clay stabilizer composition
or mixture.
[0097] A drilling fluid, also known as a drilling mud or simply
"mud," is a specially designed fluid that is circulated through a
wellbore as the wellbore is being drilled to facilitate the
drilling operation. The drilling fluid can be water-based or
oil-based. The drilling fluid can carry cuttings up from beneath
and around the bit, transport them up the annulus, and allow their
separation. Also, a drilling fluid can cool and lubricate the drill
bit as well as reduce friction between the drill string and the
sides of the hole. The drilling fluid aids in support of the drill
pipe and drill bit, and provides a hydrostatic head to maintain the
integrity of the wellbore walls and prevent well blowouts. Specific
drilling fluid systems can be selected to optimize a drilling
operation in accordance with the characteristics of a particular
geological formation. The drilling fluid can be formulated to
prevent unwanted influxes of formation fluids from permeable rocks
and also to form a thin, low permeability filter cake that
temporarily seals pores, other openings, and formations penetrated
by the bit. In water-based drilling fluids, solid particles are
suspended in a water or brine solution containing other components.
Oils or other non-aqueous liquids can be emulsified in the water or
brine or at least partially solubilized (for less hydrophobic
non-aqueous liquids), but water is the continuous phase. A drilling
fluid can be present in the clay stabilizer composition or a
mixture including the same in any suitable amount, such as about 1
wt % or less, about 2 wt %, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60,
70, 80, 85, 90, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt
% or more.
[0098] A water-based drilling fluid in embodiments of the present
invention can be any suitable water-based drilling fluid. In
various embodiments, the drilling fluid can include at least one of
water (fresh or brine), a salt (e.g., calcium chloride, sodium
chloride, potassium chloride, magnesium chloride, calcium bromide,
sodium bromide, potassium bromide, calcium nitrate, sodium formate,
potassium formate, cesium formate), aqueous base (e.g., sodium
hydroxide or potassium hydroxide), alcohol or polyol, cellulose,
starches, alkalinity control agents, density control agents such as
a density modifier (e.g., barium sulfate), surfactants (e.g.,
betaines, alkali metal alkylene acetates, sultaines, ether
carboxylates), emulsifiers, dispersants, polymeric stabilizers,
crosslinking agents, polyacrylamides, polymers or combinations of
polymers, antioxidants, heat stabilizers, foam control agents,
solvents, diluents, plasticizers, filler or inorganic particles
(e.g., silica), pigments, dyes, precipitating agents (e.g.,
silicates or aluminum complexes), and rheology modifiers such as
thickeners or viscosifiers (e.g., xanthan gum). Any ingredient
listed in this paragraph can be either present or not present in
the mixture.
[0099] An oil-based drilling fluid or mud in embodiments of the
present invention can be any suitable oil-based drilling fluid. In
various embodiments, the drilling fluid can include at least one of
an oil-based fluid (or synthetic fluid), saline, aqueous solution,
emulsifiers, other agents or additives for suspension control,
weight or density control, oil-wetting agents, fluid loss or
filtration control agents, and rheology control agents. An
oil-based or invert emulsion-based drilling fluid can include
between about 10:90 to about 95:5, or about 50:50 to about 95:5, by
volume of oil phase to water phase. A substantially all oil mud
includes about 100% liquid phase oil by volume (e.g., substantially
no internal aqueous phase).
[0100] A pill is a relatively small quantity (e.g., less than about
500 bbl, or less than about 200 bbl) of drilling fluid used to
accomplish a specific task that the regular drilling fluid cannot
perform. For example, a pill can be a high-viscosity pill to, for
example, help lift cuttings out of a vertical wellbore. In another
example, a pill can be a freshwater pill to, for example, dissolve
a salt formation. Another example is a pipe-freeing pill to, for
example, destroy filter cake and relieve differential sticking
forces. In another example, a pill is a lost circulation material
pill to, for example, plug a thief zone. A pill can include any
component described herein as a component of a drilling fluid.
[0101] A cement fluid can include an aqueous mixture of at least
one of cement and cement kiln dust. The clay stabilizer composition
can form a useful combination with cement or cement kiln dust. The
cement kiln dust can be any suitable cement kiln dust. Cement kiln
dust can be formed during the manufacture of cement and can be
partially calcined kiln feed that is removed from the gas stream
and collected in a dust collector during a manufacturing process.
Cement kiln dust can be advantageously utilized in a cost-effective
manner since kiln dust is often regarded as a low value waste
product of the cement industry. Some embodiments of the cement
fluid can include cement kiln dust but no cement, cement kiln dust
and cement, or cement but no cement kiln dust. The cement can be
any suitable cement. The cement can be a hydraulic cement. A
variety of cements can be utilized in accordance with embodiments
of the present invention; for example, those including calcium,
aluminum, silicon, oxygen, iron, or sulfur, which can set and
harden by reaction with water. Suitable cements can include
Portland cements, pozzolana cements, gypsum cements, high alumina
content cements, slag cements, silica cements, and combinations
thereof. In some embodiments, the Portland cements that are
suitable for use in embodiments of the present invention are
classified as Classes A, C, H, and G cements according to the
American Petroleum Institute, API Specification for Materials and
Testing for Well Cements, API Specification 10, Fifth Ed., Jul. 1,
1990. A cement can be generally included in the cementing fluid in
an amount sufficient to provide the desired compressive strength,
density, or cost. In some embodiments, the hydraulic cement can be
present in the cementing fluid in an amount in the range of from 0
wt % to about 100 wt %, about 0 wt % to about 95 wt %, about 20 wt
% to about 95 wt %, or about 50 wt % to about 90 wt %. A cement
kiln dust can be present in an amount of at least about 0.01 wt %,
or about 5 wt % to about 80 wt %, or about 10 wt % to about 50 wt
%.
[0102] Optionally, other additives can be added to a cement or kiln
dust-containing composition of embodiments of the present invention
as deemed appropriate by one skilled in the art, with the benefit
of this disclosure. Any optional ingredient listed in this
paragraph can be either present or not present in the clay
stabilizer composition or a mixture including the same. For
example, the clay stabilizer composition can include fly ash,
metakaolin, shale, zeolite, set retarding additive, surfactant, a
gas, accelerators, weight reducing additives, heavy-weight
additives, lost circulation materials, filtration control
additives, dispersants, and combinations thereof. In some examples,
additives can include crystalline silica compounds, amorphous
silica, salts, fibers, hydratable clays, microspheres, pozzolan
lime, thixotropic additives, combinations thereof, and the
like.
[0103] In various embodiments, the clay stabilizer composition or
mixture can include a proppant, a resin-coated proppant, an
encapsulated resin, or a combination thereof. A proppant is a
material that keeps an induced hydraulic fracture at least
partially open during or after a fracturing treatment. Proppants
can be transported into the subterranean formation (e.g., downhole)
to the fracture using fluid, such as fracturing fluid or another
fluid. A higher-viscosity fluid can more effectively transport
proppants to a desired location in a fracture, especially larger
proppants, by more effectively keeping proppants in a suspended
state within the fluid. Examples of proppants can include sand,
gravel, glass beads, polymer beads, ground products from shells and
seeds such as walnut hulls, and manmade materials such as ceramic
proppant, bauxite, tetrafluoroethylene materials (e.g., TEFLON.TM.
polytetrafluoroethylene), fruit pit materials, processed wood,
composite particulates prepared from a binder and fine grade
particulates such as silica, alumina, fumed silica, carbon black,
graphite, mica, titanium dioxide, meta-silicate, calcium silicate,
kaolin, talc, zirconia, boron, fly ash, hollow glass microspheres,
and solid glass, or mixtures thereof. In some embodiments, the
proppant can have an average particle size, wherein particle size
is the largest dimension of a particle, of about 0.001 mm to about
3 mm, about 0.15 mm to about 2.5 mm, about 0.25 mm to about 0.43
mm, about 0.43 mm to about 0.85 mm, about 0.0001 mm to about 3 mm,
about 0.015 mm to about 2.5 mm, about 0.025 mm to about 0.43 mm,
about 0.043 mm to about 0.85 mm, about 0.085 mm to about 1.18 mm,
about 0.85 mm to about 1.18 mm, about 1.18 mm to about 1.70 mm, or
about 1.70 to about 2.36 mm. In some embodiments, the proppant can
have a distribution of particle sizes clustering around multiple
averages, such as one, two, three, or four different average
particle sizes. The clay stabilizer composition or mixture can
include any suitable amount of proppant, such as about 0.01 wt % to
about 99.99 wt %, about 0.1 wt % to about 80 wt %, about 10 wt % to
about 60 wt %, or about 0.01 wt % or less, or about 0.1 wt %, 1, 2,
3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93,
94, 95, 96, 97, 98, 99, about 99.9 wt %, or about 99.99 wt % or
more.
Drilling Assembly.
[0104] In various embodiments, the silane-functionalized PAI clay
stabilizer or clay stabilizer composition including the same can
directly or indirectly affect one or more components or pieces of
equipment associated with the preparation, delivery, recapture,
recycling, reuse, and/or disposal of the disclosed
silane-functionalized PAI clay stabilizer or clay stabilizer
composition including the same. For example, and with reference to
FIG. 1, the silane-functionalized PAI clay stabilizer or clay
stabilizer composition including the same can directly or
indirectly affect one or more components or pieces of equipment
associated with an exemplary wellbore drilling assembly 100,
according to one or more embodiments. It should be noted that while
FIG. 1 generally depicts a land-based drilling assembly, those
skilled in the art will readily recognize that the principles
described herein are equally applicable to subsea drilling
operations that employ floating or sea-based platforms and rigs,
without departing from the scope of the disclosure.
[0105] As illustrated, the drilling assembly 100 can include a
drilling platform 102 that supports a derrick 104 having a
traveling block 106 for raising and lowering a drill string 108.
The drill string 108 can include drill pipe and coiled tubing, as
generally known to those skilled in the art. A kelly 110 supports
the drill string 108 as it is lowered through a rotary table 112. A
drill bit 114 is attached to the distal end of the drill string 108
and is driven either by a downhole motor and/or via rotation of the
drill string 108 from the well surface. As the bit 114 rotates, it
creates a wellbore 116 that penetrates various subterranean
formations 118.
[0106] A pump 120 (e.g., a mud pump) circulates drilling fluid 122
through a feed pipe 124 and to the kelly 110, which conveys the
drilling fluid 122 downhole through the interior of the drill
string 108 and through one or more orifices in the drill bit 114.
The drilling fluid 122 is then circulated back to the surface via
an annulus 126 defined between the drill string 108 and the walls
of the wellbore 116. At the surface, the recirculated or spent
drilling fluid 122 exits the annulus 126 and can be conveyed to one
or more fluid processing unit(s) 128 via an interconnecting flow
line 130. After passing through the fluid processing unit(s) 128, a
"cleaned" drilling fluid 122 is deposited into a nearby retention
pit 132 (e.g., a mud pit). While the fluid processing unit(s) 128
is illustrated as being arranged at the outlet of the wellbore 116
via the annulus 126, those skilled in the art will readily
appreciate that the fluid processing unit(s) 128 can be arranged at
any other location in the drilling assembly 100 to facilitate its
proper function, without departing from the scope of the
disclosure.
[0107] The silane-functionalized PAI clay stabilizer or clay
stabilizer composition including the same can be added to the
drilling fluid 122 via a mixing hopper 134 communicably coupled to
or otherwise in fluid communication with the retention pit 132. The
mixing hopper 134 can include mixers and related mixing equipment
known to those skilled in the art. In other embodiments, however,
the silane-functionalized PAI clay stabilizer or clay stabilizer
composition including the same can be added to the drilling fluid
122 at any other location in the drilling assembly 100. In at least
one embodiment, for example, there could be more than one retention
pit 132, such as multiple retention pits 132 in series. Moreover,
the retention pit 132 can be representative of one or more fluid
storage facilities and/or units where the silane-functionalized PAI
clay stabilizer or clay stabilizer composition including the same
can be stored, reconditioned, and/or regulated until added to the
drilling fluid 122.
[0108] As mentioned above, the silane-functionalized PAI clay
stabilizer or clay stabilizer composition including the same can
directly or indirectly affect the components and equipment of the
drilling assembly 100. For example, the silane-functionalized PAI
clay stabilizer or clay stabilizer composition including the same
can directly or indirectly affect the fluid processing unit(s) 128,
which can include one or more of a shaker (e.g., shale shaker), a
centrifuge, a hydrocyclone, a separator (including magnetic and
electrical separators), a desilter, a desander, a separator, a
filter (e.g., diatomaceous earth filters), a heat exchanger, or any
fluid reclamation equipment. The fluid processing unit(s) 128 can
further include one or more sensors, gauges, pumps, compressors,
and the like used to store, monitor, regulate, and/or recondition
the silane-functionalized PAI clay stabilizer or clay stabilizer
composition including the same.
[0109] The silane-functionalized PAI clay stabilizer or clay
stabilizer composition including the same can directly or
indirectly affect the pump 120, which representatively includes any
conduits, pipelines, trucks, tubulars, and/or pipes used to
fluidically convey the silane-functionalized PAI clay stabilizer or
clay stabilizer composition including the same to the subterranean
formation; any pumps, compressors, or motors (e.g., topside or
downhole) used to drive the composition into motion; any valves or
related joints used to regulate the pressure or flow rate of the
composition; and any sensors (e.g., pressure, temperature, flow
rate, and the like), gauges, and/or combinations thereof, and the
like. The silane-functionalized PAI clay stabilizer or clay
stabilizer composition including the same can also directly or
indirectly affect the mixing hopper 134 and the retention pit 132
and their assorted variations.
[0110] The silane-functionalized PAI clay stabilizer or clay
stabilizer composition including the same can also directly or
indirectly affect the various downhole or subterranean equipment
and tools that can come into contact with the silane-functionalized
PAI clay stabilizer or clay stabilizer composition including the
same such as the drill string 108, any floats, drill collars, mud
motors, downhole motors, and/or pumps associated with the drill
string 108, and any measurement while drilling (MWD)/logging while
drilling (LWD) tools and related telemetry equipment, sensors, or
distributed sensors associated with the drill string 108. The
silane-functionalized PAI clay stabilizer or clay stabilizer
composition including the same can also directly or indirectly
affect any downhole heat exchangers, valves, and corresponding
actuation devices, tool seals, packers, and other wellbore
isolation devices or components, and the like associated with the
wellbore 116. The silane-functionalized PAI clay stabilizer or clay
stabilizer composition including the same can also directly or
indirectly affect the drill bit 114, which can include roller cone
bits, polycrystalline diamond compact (PDC) bits, natural diamond
bits, hole openers, reamers, coring bits, and the like.
[0111] While not specifically illustrated herein, the
silane-functionalized PAI clay stabilizer or clay stabilizer
composition including the same can also directly or indirectly
affect any transport or delivery equipment used to convey the clay
stabilizer or the composition including the same to the drilling
assembly 100 such as, for example, any transport vessels, conduits,
pipelines, trucks, tubulars, and/or pipes used to fluidically move
the clay stabilizer or composition from one location to another;
any pumps, compressors, or motors used to drive the clay stabilizer
composition into motion; any valves or related joints used to
regulate the pressure or flow rate of the clay stabilizer
composition; and any sensors (e.g., pressure and temperature),
gauges, and/or combinations thereof, and the like.
System or Apparatus.
[0112] In various embodiments, the present invention provides a
system. The system can be any suitable system that can use or that
can be generated by use of an embodiment of the clay stabilizer
composition described herein in a subterranean formation, or that
can perform or be generated by performance of a method for using
the clay stabilizer composition described herein.
[0113] The system can include a tubular disposed in a subterranean
formation. The system can include a pump configured to pump a clay
stabilizer composition including a silane-functionalized PAI clay
stabilizer in the subterranean formation through the tubular.
[0114] The system can include a clay stabilizer composition
including a silane-functionalized PAI clay stabilizer. The system
can also include a subterranean formation including the clay
stabilizer composition therein. In some embodiments, the clay
stabilizer composition in the system can also include a downhole
fluid, or the system can include a mixture of the clay stabilizer
composition and downhole fluid. In some embodiments, the system can
include a tubular, and a pump configured to pump the clay
stabilizer composition into the subterranean formation through the
tubular.
[0115] Various embodiments provide systems and apparatus configured
for delivering the clay stabilizer composition described herein to
a subterranean location and for using the clay stabilizer
composition therein, such as for a drilling operation, or a
fracturing operation (e.g., pre-pad, pad, slurry, or finishing
stages). In various embodiments, the system or apparatus can
include a pump fluidly coupled to a tubular (e.g., any suitable
type of oilfield pipe, such as pipeline, drill pipe, production
tubing, and the like), with the tubular containing a clay
stabilizer composition including the silane-functionalized PAI clay
stabilizer described herein.
[0116] In some embodiments, the system can include a drill string
disposed in a wellbore, with the drill string including a drill bit
at a downhole end of the drill string. The system can also include
an annulus between the drill string and the wellbore. The system
can also include a pump configured to circulate the clay stabilizer
composition through the drill string, through the drill bit, and
back above-surface through the annulus. In some embodiments, the
system can include a fluid processing unit configured to process
the clay stabilizer composition exiting the annulus to generate a
cleaned drilling fluid for recirculation through the wellbore.
[0117] The pump can be a high pressure pump in some embodiments. As
used herein, the term "high pressure pump" will refer to a pump
that is capable of delivering a fluid to a subterranean formation
(e.g., downhole) at a pressure of about 1000 psi or greater. A high
pressure pump can be used when it is desired to introduce the clay
stabilizer composition to a subterranean formation at or above a
fracture gradient of the subterranean formation, but it can also be
used in cases where fracturing is not desired. In some embodiments,
the high pressure pump can be capable of fluidly conveying
particulate matter, such as proppant particulates, into the
subterranean formation. Suitable high pressure pumps will be known
to one having ordinary skill in the art and can include floating
piston pumps and positive displacement pumps.
[0118] In other embodiments, the pump can be a low pressure pump.
As used herein, the term "low pressure pump" will refer to a pump
that operates at a pressure of about 1000 psi or less. In some
embodiments, a low pressure pump can be fluidly coupled to a high
pressure pump that is fluidly coupled to the tubular. That is, in
such embodiments, the low pressure pump can be configured to convey
the clay stabilizer composition to the high pressure pump. In such
embodiments, the low pressure pump can "step up" the pressure of
the clay stabilizer composition before it reaches the high pressure
pump.
[0119] In some embodiments, the systems or apparatuses described
herein can further include a mixing tank that is upstream of the
pump and in which the clay stabilizer composition is formulated. In
various embodiments, the pump (e.g., a low pressure pump, a high
pressure pump, or a combination thereof) can convey the clay
stabilizer composition from the mixing tank or other source of the
clay stabilizer composition to the tubular. In other embodiments,
however, the clay stabilizer composition can be formulated offsite
and transported to a worksite, in which case the clay stabilizer
composition can be introduced to the tubular via the pump directly
from its shipping container (e.g., a truck, a railcar, a barge, or
the like) or from a transport pipeline. In either case, the clay
stabilizer composition can be drawn into the pump, elevated to an
appropriate pressure, and then introduced into the tubular for
delivery to the subterranean formation.
[0120] FIG. 2 shows an illustrative schematic of systems and
apparatuses that can deliver embodiments of the clay stabilizer
compositions of the present invention to a subterranean location,
according to one or more embodiments. It should be noted that while
FIG. 2 generally depicts a land-based system or apparatus, it is to
be recognized that like systems and apparatuses can be operated in
subsea locations as well. Embodiments of the present invention can
have a different scale than that depicted in FIG. 2. As depicted in
FIG. 2, system or apparatus 1 can include mixing tank 10, in which
an embodiment of the clay stabilizer composition can be formulated.
The clay stabilizer composition can be conveyed via line 12 to
wellhead 14, where the clay stabilizer composition enters tubular
16, with tubular 16 extending from wellhead 14 into subterranean
formation 18. Upon being ejected from tubular 16, the clay
stabilizer composition can subsequently penetrate into subterranean
formation 18. Pump 20 can be configured to raise the pressure of
the clay stabilizer composition to a desired degree before its
introduction into tubular 16. It is to be recognized that system or
apparatus 1 is merely exemplary in nature and various additional
components can be present that have not necessarily been depicted
in FIG. 2 in the interest of clarity. In some examples, additional
components that can be present include supply hoppers, valves,
condensers, adapters, joints, gauges, sensors, compressors,
pressure controllers, pressure sensors, flow rate controllers, flow
rate sensors, temperature sensors, and the like.
[0121] Although not depicted in FIG. 2, at least part of the clay
stabilizer composition can, in some embodiments, flow back to
wellhead 14 and exit subterranean formation 18. The clay stabilizer
composition that flows back can be substantially diminished in the
concentration of the silane-functionalized PAI clay stabilizer
therein. In some embodiments, the clay stabilizer composition that
has flowed back to wellhead 14 can subsequently be recovered, and
in some examples reformulated, and recirculated to subterranean
formation 18.
[0122] It is also to be recognized that the disclosed composition
can also directly or indirectly affect the various downhole or
subterranean equipment and tools that can come into contact with
the clay stabilizer composition during operation. Such equipment
and tools can include wellbore casing, wellbore liner, completion
string, insert strings, drill string, coiled tubing, slickline,
wireline, drill pipe, drill collars, mud motors, downhole motors
and/or pumps, surface-mounted motors and/or pumps, centralizers,
turbolizers, scratchers, floats (e.g., shoes, collars, valves, and
the like), logging tools and related telemetry equipment, actuators
(e.g., electromechanical devices, hydromechanical devices, and the
like), sliding sleeves, production sleeves, plugs, screens,
filters, flow control devices (e.g., inflow control devices,
autonomous inflow control devices, outflow control devices, and the
like), couplings (e.g., electro-hydraulic wet connect, dry connect,
inductive coupler, and the like), control lines (e.g., electrical,
fiber optic, hydraulic, and the like), surveillance lines, drill
bits and reamers, sensors or distributed sensors, downhole heat
exchangers, valves and corresponding actuation devices, tool seals,
packers, cement plugs, bridge plugs, and other wellbore isolation
devices or components, and the like. Any of these components can be
included in the systems and apparatuses generally described above
and depicted in FIG. 2.
Clay Stabilizer and Composition Including the Same.
[0123] Various embodiments provide a silane-functionalized clay
stabilizer or a clay stabilizer composition including the same for
treatment of a subterranean formation. The clay stabilizer or clay
stabilizer composition can be any suitable clay stabilizer or clay
stabilizer composition that can be used to perform an embodiment of
the method for treatment of a subterranean formation described
herein. For example, the clay stabilizer can be a
silane-functionalized PAI clay stabilizer for treatment of a
subterranean formation.
[0124] In some embodiments, the clay stabilizer composition further
include, or can be, a downhole fluid. The downhole fluid can be any
suitable downhole fluid. In some embodiments, the downhole fluid
can be a drilling fluid or a fracturing fluid.
[0125] In various embodiments, the present invention provides a
silane-functionalized polyalkyleneimine (PAI) clay stabilizer for
treatment of a subterranean formation, wherein the
silane-functionalized PAI clay stabilizer is a polymer including a
repeating unit having the following structure:
##STR00012##
At each occurrence of R.sup.1 and D in the same repeating unit, a)
R.sup.1 can be independently selected from the group consisting of
--H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and D is H, or b)
R.sup.1 and D together in the same repeating unit can form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.1 is bound.
At each occurrence, X can be independently selected from the group
consisting of --(CH.sub.2).sub.2--O--, --(CH.sub.2).sub.3--O--,
--(CH.sub.2).sub.2--S--, --(CH.sub.2).sub.3--S--, and a
--(C.sub.1-10)alkylene-. At each occurrence, m can be about 0 to
about 10. At each occurrence, Li can be a substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbylene interrupted by 0, 1,
2, or 3 groups independently selected from --O--, --S--, and
substituted or unsubstituted --NH--. At each occurrence, R.sup.A
can be independently selected from --O--R.sup.B, --H, and
--R.sup.B, wherein at least one R.sup.A of each
--Si--(R.sup.A).sub.3 is --O--R.sup.B. At each occurrence, R.sup.B
can be independently substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl. At each occurrence of R.sup.2 and E
in the same R.sup.1 or in the same R.sup.3, a) R.sup.2 can be
independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHF--N(R.sup.3).sub.2, and E is H, or b)
R.sup.2 and E together in the same R.sup.1 or in the same R.sup.3
can form a (C.sub.1-C.sub.10)heterocycle with the N to which
R.sup.2 is bound. At each occurrence of R.sup.3 and F in the same
R.sup.2, a) R.sup.3 is independently selected from the group
consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and F is H, or b)
R.sup.3 and F together in the same R.sup.2 form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.3 is bound.
At one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, and R.sup.3 in the silane-functionalized PAI clay
stabilizer molecule is a silicon-containing group. Each amine group
can be independently in the form of a neutral amine or a protonated
cationic amine. Various embodiments provide a clay stabilizer
composition including the silane-functionalized PAI clay
stabilizer.
[0126] In some embodiments, the present invention provides a
silane-functionalized PEI clay stabilizer for treatment of a
subterranean formation, wherein the silane-functionalized PEI clay
stabilizer is a polymer including a repeating unit having the
following structure:
##STR00013##
At each occurrence, R.sup.1 can be independently selected from the
group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At each occurrence, L.sup.1
can be a substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbylene interrupted by 0, 1, 2, or 3
groups independently selected from --O--, --S--, and substituted or
unsubstituted --NH--. At each occurrence, R.sup.A can be
independently selected from --O--R.sup.B, --H, and --R.sup.B,
wherein at least one R.sup.A of each --Si--(R.sup.A).sub.3 is
--O--R.sup.B. At each occurrence, R.sup.B can be independently
substituted or unsubstituted (C.sub.1-C.sub.20)hydrocarbyl. At each
occurrence, R.sup.2 can be independently selected from the group
consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2. At each occurrence, R.sup.3
can be independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At one or more occurrences,
at least one group selected from R.sup.1, R.sup.2, and R.sup.3 in
the silane-functionalized PEI clay stabilizer molecule can be a
silicon-containing group. Each amine group can be independently in
the form of a neutral amine or a protonated cationic amine. Various
embodiments provide a clay stabilizer composition including the
silane-functionalized PEI clay stabilizer.
[0127] Various embodiments provide a silane-functionalized PEI clay
stabilizer for treatment of a subterranean formation, wherein the
silane-functionalized PEI clay stabilizer has the structure:
##STR00014##
Each amine group is independently in the form of a neutral amine or
a protonated cationic amine. At each occurrence, R.sup.1 can be
independently selected from the group consisting of --H,
--CH.sub.2--CH(OH)--(C.sub.1-C.sub.5)alkylene-O--(C.sub.1-C.sub.10)alkyle-
ne-Si(0-(C.sub.1-C.sub.10)alkyl).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, wherein at each occurrence,
each (C.sub.1-C.sub.10)alkylene, (C.sub.1-C.sub.5)alkylene, and
(C.sub.1-C.sub.10)alkyl is independently selected. At each
occurrence, R.sup.2 can be independently selected from the group
consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2. At each occurrence, R.sup.3
can be independently selected from the group consisting of --H,
-L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At each occurrence, R.sup.4
can be independently selected from the group consisting of --H and
-L.sup.1-Si--(R.sup.A).sub.3. At one or more occurrences, at least
one group selected from R.sup.1, R.sup.2, R.sup.3, and R.sup.4 in
the silane-functionalized PEI clay stabilizer molecule can be a
silicon-containing group. The variable n can be about 2 to about
1,000,000. Various embodiments provide a clay stabilizer
composition including the silane-functionalized PEI clay
stabilizer.
Method for Preparing a Clay Stabilizer or Composition Including the
Same for Treatment of a Subterranean Formation.
[0128] In various embodiments, the present invention provides a
method for preparing a silane-functionalized PAI clay stabilizer or
clay stabilizer composition including the same for treatment of a
subterranean formation. The method can be any suitable method that
produces a silane-functionalized PAI clay stabilizer or clay
stabilizer composition including the same described herein. In some
embodiments, the method can include combining various components of
the composition to form the clay stabilizer composition. In some
embodiments, the method can include forming the
silane-functionalized PAI clay stabilizer.
[0129] In some embodiments, the present invention provides a method
of preparing a silane-functionalized PAI clay stabilizer for
treatment of a subterranean formation. The method can include
forming a mixture including a silane-functionalized epoxide and a
PAI. The method can also include allowing the mixture to react to
form the silane-functionalized PAI clay stabilizer. In some
embodiments, the method can include forming a clay stabilizer
composition including the silane-functionalized PAI clay
stabilizer, such as by combining the silane-functionalized clay
stabilizer to one or more other components to form the clay
stabilizer composition.
[0130] The PAI can be a polymer including a repeating unit having
the structure:
##STR00015##
At each occurrence of R.sup.1 and D in the same repeating unit, a)
R.sup.1 can be independently selected from the group consisting of
--H and --(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and D is H, or
b) R.sup.1 and D together in the same repeating unit can form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.1 is bound.
At each occurrence, X can be independently selected from the group
consisting of --(CH.sub.2).sub.2--O--, --(CH.sub.2).sub.3--O--,
--(CH.sub.2).sub.2--S--, --(CH.sub.2).sub.3--S--, and a
--(C.sub.1-10)alkylene-. At each occurrence, m can be about 0 to
about 10. At each occurrence of R.sup.2 and E in the same R.sup.1
or in the same R.sup.3, a) R.sup.2 can be independently selected
from the group consisting of --H and
--(X).sub.m--CH.sub.2--CHF--N(R.sup.3).sub.2, and E is H, or b)
R.sup.2 and E together in the same R.sup.1 or in the same R.sup.3
can form a (C.sub.1-C.sub.10)heterocycle with the N to which
R.sup.2 is bound. At each occurrence of R.sup.3 and F in the same
R.sup.2, a) R.sup.3 can be independently selected from the group
consisting of --H and --(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2,
and F is H, or b) R.sup.3 and F together in the same R.sup.2 can
form a (C.sub.1-C.sub.10)heterocycle with the N to which R.sup.3 is
bound. Each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0131] The silane-functionalized PAI clay stabilizer can have the
structure:
##STR00016##
At each occurrence of R.sup.4 in an end group not including G,
R.sup.4 can be independently selected from the group consisting of
--H and -L.sup.1-Si--(R.sup.A).sub.3. At each occurrence of R.sup.4
and G in the same end group, a) R.sup.4 can be independently
selected from the group consisting of --H and
-L.sup.1-Si--(R.sup.A).sub.3 and G is H, or b) R.sup.4 and G
together in the same end group can form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.4 is bound.
The variable n is about 2 to about 1,000,000, about 2 to about
1,000, about 2 to about 100, or about 2, or less than, equal to, or
greater than 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24,
26, 28, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 90, 100, 125,
150, 175, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900,
1,000, 1,500, 2,000, 2,500, 5,000, 10,000, 20,000, 50,000, 100,000,
500,000, or about 1,000,000 or more. Each amine group can be
independently in the form of a neutral amine or a protonated
cationic amine.
[0132] The PAI can be a PEI. The variable m can be 0. The variables
D, E, F, and G can be H. The PEI can be a polymer including a
repeating unit having the structure:
##STR00017##
Each amine group is independently in the form of a neutral amine or
a protonated cationic amine. At each occurrence, R.sup.1 can be
independently selected from the group consisting of --H and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At each occurrence, R.sup.2
can be independently selected from the group consisting of --H, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2. At each occurrence, R.sup.3
can be independently selected from the group consisting of --H, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2. At one or more occurrences,
at least one group selected from R.sup.1, R.sup.2, and R.sup.3 in
the silane-functionalized PEI clay stabilizer molecule can be a
silicon-containing group.
[0133] The PAI can have the structure:
##STR00018##
Each amine group is independently in the form of a neutral amine or
a protonated cationic amine. The variable n is about 2 to about
1,000,000, about 2 to about 1,000, about 2 to about 100, or about
2, or less than, equal to, or greater than 3, 4, 5, 6, 7, 8, 9, 10,
12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 35, 40, 45, 50, 55, 60, 65,
70, 75, 80, 90, 100, 125, 150, 175, 200, 250, 300, 350, 400, 450,
500, 600, 700, 800, 900, 1,000, 1,500, 2,000, 2,500, 5,000, 10,000,
20,000, 50,000, 100,000, 500,000, or about 1,000,000 or more.
[0134] The silane-functionalized epoxide can have the
structure:
##STR00019##
At each occurrence, L.sup.1A can be a substituted or unsubstituted
(C.sub.1-C.sub.20)alkylene interrupted by --O--. At each
occurrence, R.sup.A can be independently selected from
--O--R.sup.B, --H, and --R.sup.B, wherein at least one R.sup.A of
each --Si--(R.sup.A).sub.3 is --O--R.sup.B. At each occurrence,
R.sup.B can be independently substituted or unsubstituted
(C.sub.1-C.sub.20)hydrocarbyl. At each occurrence, L.sup.1A can
independently have the structure -L.sup.2A-O-L.sup.3A-. At each
occurrence, L.sup.2A can be independently a substituted or
unsubstituted (C.sub.1-C.sub.10)alkylene. At each occurrence,
L.sup.2A can be independently an unsubstituted
(C.sub.1-C.sub.5)alkylene. At each occurrence, L.sup.3A can be
independently a substituted or unsubstituted
(C.sub.1-C.sub.10)alkylene. At each occurrence, L.sup.3A can be
--CH.sub.2--. The variable L.sup.1A can be:
##STR00020##
[0135] The variable R.sup.A can be --O--R.sup.B. At each
occurrence, the variable R.sup.B can be independently
(C.sub.1-C.sub.20)alkyl. At each occurrence, the variable R.sup.B
can be independently (C.sub.1-C.sub.5)alkyl. The variable R.sup.B
can be methyl. The silane-functionalized epoxide can have the
structure:
##STR00021##
[0136] The molar ratio of the silane-functionalized epoxide to the
number of PAI repeating groups in the PAI can be any suitable
ratio, such as about 1:100,000 to about 100:1, about 2:1 to about
6:1, about 1:100,000 or less, or less than, equal to, or more than
about 1:50,000, 1:10,000, 1:5,000, 1:2,500, 1:1,000, 1:500, 1:250,
1:100, 1:50, 1:25, 1:10, 1:8, 1:6, 1:4, 1:2, 1:1, 1.5:1, 2:1,
2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 7:1, 8:1, 9:1,
10:1, 12:1, 14:1, 16:1, 20:1, 25:1, 50:1, 75:1, or about 100:1 or
more.
[0137] The mixture including the silane-functionalized epoxide and
the PAI can have any suitable pH during the reaction, such as about
6 to about 13, about 7 to about 12, about 8 to about 10, or about 6
or less, or less than, equal to, or more than about 6.5, 7, 7.5, 8,
8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, or about 13 or more.
EXAMPLES
[0138] Various embodiments of the present invention can be better
understood by reference to the following Examples which are offered
by way of illustration. The present invention is not limited to the
Examples given herein.
Example 1. Synthesis of Clay Stabilizer
[0139] An aqueous solution was prepared containing 1% v/v branched
polyethyleneimine (PEI) (MW 800) by adding 1 mL of PEI at constant
stirring and room temperature to a flask containing 100 mL of
distilled water. The pH of the solution was adjusted to 9 using
NaOH. Then, at room temperature, 1 mL of
3-glycidoxypropyltrimethoxysilane was added directly to the already
prepared 100 mL of PEI solution, with shaking, to form a solution
containing a silane-functionalized clay stabilizer. No purification
or neutralization procedure was performed. The solution was freshly
used for subsequent Examples.
[0140] FIG. 3 illustrates a reaction scheme illustrating the
reaction generally. FIG. 4 illustrates proposed electrostatic and
covalent bonding mechanisms for interaction of the clay stabilizer
with clay surfaces.
Example 2. Clay Stabilization Testing
[0141] Two conventional tests were performed: a fines generation
test using 20% illite clay and a clay swelling test using 8%
bentonite clay. Two conventional tests were performed: a fines
generation test using 20% illite clay and a clay swelling test
using 8% bentonite clay. The fines generation test rotated
end-over-end a 20% illite sample in a fluid for 0, 10, and 120
minutes at 15 revolutions per minute. A light source was then used
on the sample to determine the amount of suspended fine materials
released from the illite sample due to migration. When a sample is
exposed to different treatments, more or less fines are generated,
resulting in a measurement of fines in the fluid sample. The clay
swelling test (CST) used capillary suction time to determine the
extent of swelling of an 8% bentonite clay sample in a fluid slurry
after different treatments. A swelling sample has less free water
and a lower permeability in the filter cake resulting in a longer
CST time; when the sample is exposed to treatments that prevent
clay swelling the CST will decrease.
[0142] The tests were performed using deionized water (DI),
Clayfix.TM. 3, Cla-Sta.COPYRGT. XP, Cla-Sta.COPYRGT. FS,
Cla-Web.TM., 7% KCl, and the clay stabilizer of Example 1 (0.5 wt %
aqueous solution). The Clayfix.TM. 3, Cla-Sta.COPYRGT. XP,
Cla-Sta.COPYRGT. FS, Cla-Web.TM. were used as 0.1 wt % aqueous
solutions for the fines generation test, and as 0.01 wt % solutions
for the clay swelling test. The 0.1 wt % of Cla-Sta.COPYRGT. XP,
Cla-Sta.COPYRGT. FS, Cla-Web.TM. were saturated solutions that were
expected to have the same effects in the fines generation test as
solutions having higher concentrations of these products. The
results of the tests are illustrated in FIG. 5. Lower numbers
indicate better results. The clay stabilizer of Example 1 protected
against fines generation better than 7% KCl, Clayfix.TM. 3, and
Cla-Web.TM., and had similar protection to Cla-Sta.COPYRGT. XP but
with more expected permanency. Through modifications to the
concentration, molecular weight, functionalization, or a
combination thereof, the clay stabilizer of Example 1 could provide
fines control, swelling control, or both, on-par or better than
that provided by Cla-Sta.COPYRGT. FS.
[0143] Based on the results, and the added permanency, the clay
stabilizer of Example 1 is an effective solution for targeting
fines control in fluid-sensitive formations.
[0144] The terms and expressions that have been employed are used
as terms of description and not of limitation, and there is no
intention in the use of such terms and expressions of excluding any
equivalents of the features shown and described or portions
thereof, but it is recognized that various modifications are
possible within the scope of the embodiments of the present
invention. Thus, it should be understood that although the present
invention has been specifically disclosed by specific embodiments
and optional features, modification and variation of the concepts
herein disclosed may be resorted to by those of ordinary skill in
the art, and that such modifications and variations are considered
to be within the scope of embodiments of the present invention.
Additional Embodiments
[0145] The following exemplary embodiments are provided, the
numbering of which is not to be construed as designating levels of
importance:
[0146] Embodiment 1 provides a method of treating a subterranean
formation, the method comprising:
[0147] placing in the subterranean formation a
silane-functionalized polyalkyleneimine (PAI) clay stabilizer.
[0148] Embodiment 2 provides the method of Embodiment 1, wherein a
clay stabilizer composition includes the silane-functionalized PAI
clay stabilizer, wherein placing the silane-functionalized PAI clay
stabilizer in the subterranean formation comprises placing the clay
stabilizer composition in the subterranean formation.
[0149] Embodiment 3 provides the method of Embodiment 2, wherein
the method further comprises obtaining or providing the
composition, wherein the obtaining or providing of the composition
occurs above-surface.
[0150] Embodiment 4 provides the method of any one of Embodiments
2-3, wherein the method further comprises obtaining or providing
the composition, wherein the obtaining or providing of the
composition occurs in the subterranean formation.
[0151] Embodiment 5 provides the method of any one of Embodiments
2-4, wherein at least one of prior to, during, and after the
placing of the clay stabilizer composition in the subterranean
formation, the clay stabilizer composition is used in the
subterranean formation, at least one of alone and in combination
with other materials, as a drilling fluid, stimulation fluid,
fracturing fluid, spotting fluid, clean-up fluid, completion fluid,
remedial treatment fluid, abandonment fluid, pill, acidizing fluid,
cementing fluid, packer fluid, logging fluid, or a combination
thereof.
[0152] Embodiment 6 provides the method of any one of Embodiments
2-5, further comprising combining the silane-functionalized PAI
clay stabilizer with an aqueous or oil-based fluid comprising a
drilling fluid, stimulation fluid, fracturing fluid, spotting
fluid, clean-up fluid, completion fluid, remedial treatment fluid,
abandonment fluid, pill, acidizing fluid, cementing fluid, packer
fluid, logging fluid, or a combination thereof, to form the clay
stabilizer composition.
[0153] Embodiment 7 provides the method of any one of Embodiments
2-6, wherein the clay stabilizer composition is oil- or
water-based.
[0154] Embodiment 8 provides the method of any one of Embodiments
2-7, wherein the clay stabilizer composition is a water- or
oil-based emulsion.
[0155] Embodiment 9 provides the method of Embodiment 8, wherein
the silane-functionalized PAI clay stabilizer is at least partially
dissolved in the water-phase of the emulsion.
[0156] Embodiment 10 provides the method of any one of Embodiments
2-9, wherein the clay stabilizer composition comprises a carrier
fluid.
[0157] Embodiment 11 provides the method of Embodiment 10, wherein
the carrier fluid is about 0.001 wt % to about 99.999 wt % of the
clay stabilizer composition.
[0158] Embodiment 12 provides the method of any one of Embodiments
10-11, wherein the carrier fluid is about 50 wt % to about 99.999
wt % of the clay stabilizer composition.
[0159] Embodiment 13 provides the method of any one of Embodiments
10-12, wherein the silane-functionalized PAI clay stabilizer is
dispersed or dissolved in the carrier fluid.
[0160] Embodiment 14 provides the method of any one of Embodiments
1-13, wherein the silane-functionalized PAI clay stabilizer forms
silyl bonds to clay in the subterranean formation.
[0161] Embodiment 15 provides the method of any one of Embodiments
1-14, wherein the silane-functionalized PAI clay stabilizer
provides reduced clay swelling, reduced clay migration, reduced
fines migration, or a combination thereof.
[0162] Embodiment 16 provides the method of any one of Embodiments
2-15, wherein the clay stabilizer composition provides reduced clay
swelling, reduced clay migration, reduced fines migration, or a
combination thereof, as compared to a corresponding composition
free of the silane-functionalized PAI clay stabilizer or having
less of the silane-functionalized PAI clay stabilizer therein.
[0163] Embodiment 17 provides the method of any one of Embodiments
2-16, wherein about 0.000.1 wt % to about 99.999 wt % of the
composition is the clay stabilizer.
[0164] Embodiment 18 provides the method of any one of Embodiments
2-17, wherein about 0.001 wt % to about 10 wt % of the composition
is the clay stabilizer.
[0165] Embodiment 19 provides the method of any one of Embodiments
1-18, wherein the PAI clay stabilizer is a polymer comprising a
repeating unit having the following structure:
##STR00022##
[0166] at each occurrence of R.sup.1 and D in the same repeating
unit, [0167] R.sup.1 is independently selected from the group
consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and D is H, or [0168]
R.sup.1 and D together in the same repeating unit form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.1 is
bound,
[0169] at each occurrence, X is independently selected from the
group consisting of --(CH.sub.2).sub.2--O--,
--(CH.sub.2).sub.3--O--, --(CH.sub.2).sub.2--S--,
--(CH.sub.2).sub.3--S--, and a --(C.sub.1-10)alkylene-,
[0170] at each occurrence, m is about 0 to about 10,
[0171] at each occurrence, L.sup.1 is a substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbylene interrupted by 0, 1,
2, or 3 groups independently selected from --O--, --S--, and
substituted or unsubstituted --NH--,
[0172] at each occurrence, R.sup.A is independently selected from
--O--R.sup.B, --H, and --R.sup.B, wherein at least one R.sup.A of
each --Si--(R.sup.A).sub.3 is --O--R.sup.B,
[0173] at each occurrence, R.sup.B is independently substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbyl,
[0174] at each occurrence of R.sup.2 and E in the same R.sup.1 or
in the same R.sup.3, [0175] R.sup.2 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHF--N(R.sup.3).sub.2, and E is H, or [0176]
R.sup.2 and E together in the same R.sup.1 or in the same R.sup.3
form a (C.sub.1-C.sub.10)heterocycle with the N to which R.sup.2 is
bound,
[0177] at each occurrence of R.sup.3 and F in the same R.sup.2
[0178] R.sup.3 is independently selected from the group consisting
of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and F is H, or [0179]
R.sup.3 and F together in the same R.sup.2 form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.3 is
bound,
[0180] at one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, and R.sup.3 in the silane-functionalized PAI clay
stabilizer molecule is a silicon-containing group, and
[0181] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0182] Embodiment 20 provides the method of Embodiment 19, wherein
the silane-functionalized PAI clay stabilizer has the
structure:
##STR00023##
[0183] wherein
[0184] at each occurrence of R.sup.4 in an end group not including
G, R.sup.4 is independently selected from the group consisting of
--H and -L.sup.1-Si--(R.sup.A).sub.3,
[0185] at each occurrence of R.sup.4 and G in the same end group,
[0186] R.sup.4 is independently selected from the group consisting
of --H and -L.sup.1-Si--(R.sup.A).sub.3 and G is H, or [0187]
R.sup.4 and G together in the same end group form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.4 is
bound,
[0188] n is about 2 to about 1,000,000, and
[0189] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0190] Embodiment 21 provides the method of any one of Embodiments
19-20, wherein the silane-functionalized PAI clay stabilizer is a
polyethyleneiminde (PEI) clay stabilizer, wherein at each
occurrence m is 0, and D, E, and F are H, wherein the PEI clay
stabilizer is a polymer comprising a repeating unit having the
following structure:
##STR00024##
[0191] wherein
[0192] at each occurrence, R.sup.1 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2,
[0193] at each occurrence, L.sup.1 is a substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbylene interrupted by 0, 1,
2, or 3 groups independently selected from --O--, --S--, and
substituted or unsubstituted --NH--,
[0194] at each occurrence, R.sup.A is independently selected from
--O--R.sup.B, --H, and --R.sup.B, wherein at least one R.sup.A of
each --Si--(R.sup.A).sub.3 is --O--R.sup.B,
[0195] at each occurrence, R.sup.B is independently substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbyl,
[0196] at each occurrence, R.sup.2 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2,
[0197] at each occurrence, R.sup.3 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2,
[0198] at one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, and R.sup.3 in the silane-functionalized PEI clay
stabilizer molecule is a silicon-containing group, and
[0199] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0200] Embodiment 22 provides the method of any one of Embodiments
19-21, wherein the silane-functionalized PEI clay stabilizer has
the structure:
##STR00025##
[0201] wherein
[0202] at each occurrence, R.sup.4 is independently selected from
the group consisting of --H and -L.sup.1-Si--(R.sup.A).sub.3,
[0203] n is about 2 to about 1,000,000, and
[0204] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0205] Embodiment 23 provides the method of any one of Embodiments
20-22, wherein n is about 2 to about 1,000.
[0206] Embodiment 24 provides the method of any one of Embodiments
20-23, wherein n is about 2 to about 100.
[0207] Embodiment 25 provides the method of any one of Embodiments
19-24, wherein at each occurrence, L.sup.1 is a substituted or
unsubstituted (C.sub.1-C.sub.20)alkylene interrupted by --O--.
[0208] Embodiment 26 provides the method of any one of Embodiments
19-25, wherein at each occurrence, L.sup.1 independently has the
structure -L.sup.2-O-L.sup.3-.
[0209] Embodiment 27 provides the method of Embodiment 26, wherein
at each occurrence, L.sup.2 is independently substituted or
unsubstituted (C.sub.1-C.sub.10)alkylene.
[0210] Embodiment 28 provides the method of any one of Embodiments
26-27, wherein at each occurrence, L.sup.2 is independently
unsubstituted (C.sub.1-C.sub.5)alkylene.
[0211] Embodiment 29 provides the method of any one of Embodiments
26-28, wherein at each occurrence, L.sup.3 is independently
substituted or unsubstituted (C.sub.1-C.sub.10)alkylene.
[0212] Embodiment 30 provides the method of any one of Embodiments
26-29, wherein at each occurrence, L.sup.3 is independently a
hydroxy-substituted (C.sub.1-C.sub.10)alkylene.
[0213] Embodiment 31 provides the method of any one of Embodiments
26-30, wherein at each occurrence, L.sup.3 is independently
--(C.sub.1-C.sub.5)alkylene-CH(OH)--CH.sub.2--, wherein the hydroxy
group is on the carbon beta to the amine.
[0214] Embodiment 32 provides the method of any one of Embodiments
26-31, wherein L.sup.3 is --CH.sub.2--CH(OH)--CH.sub.2--.
[0215] Embodiment 33 provides the method of any one of Embodiments
26-32, wherein L.sup.1 is
--(CH.sub.2).sub.3--O--CH.sub.2--CH(OH)--CH.sub.2--, wherein the
hydroxy group is on the carbon beta to the amine.
[0216] Embodiment 34 provides the method of any one of Embodiments
19-33, wherein R.sup.A is --O--R.sup.B.
[0217] Embodiment 35 provides the method of any one of Embodiments
19-34, wherein at each occurrence, R.sup.B is independently
(C.sub.1-C.sub.20)alkyl.
[0218] Embodiment 36 provides the method of any one of Embodiments
19-35, wherein at each occurrence, R.sup.B is independently
(C.sub.1-C.sub.5)alkyl.
[0219] Embodiment 37 provides the method of any one of Embodiments
19-36, wherein R.sup.B is methyl.
[0220] Embodiment 38 provides the method of any one of Embodiments
26-37, wherein -L.sup.1-Si--(R.sup.A).sub.3 is
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).sub.3.
[0221] Embodiment 39 provides the method of any one of Embodiments
19-38, wherein the ratio of the number of
-L.sup.1-Si--(R.sup.A).sub.3 groups in the silane-functionalized
PAI to the number of times the repeating group repeats is about
1:100,000 to about 100:1.
[0222] Embodiment 40 provides the method of any one of Embodiments
19-39, wherein the ratio of the number of
-L.sup.1-Si--(R.sup.A).sub.3 groups in the silane-functionalized
PAI to the number of times the repeating group repeats is about 2:1
to about 6:1.
[0223] Embodiment 41 provides the method of any one of Embodiments
20-40, wherein the ratio of the number of
-L.sup.1-Si--(R.sup.A).sub.3 groups in the silane-functionalized
PAI to n is about 1:100,000 to about 100:1.
[0224] Embodiment 42 provides the method of any one of Embodiments
20-41, wherein the ratio of the number of
-L.sup.1-Si--(R.sup.A).sub.3 groups in the silane-functionalized
PAI to n is about 2:1 to about 6:1.
[0225] Embodiment 43 provides the method of any one of Embodiments
1-42, wherein the silane-functionalized PAI clay stabilizer has the
structure:
##STR00026##
[0226] wherein
[0227] at each occurrence, R.sup.1 is independently selected from
the group consisting of --H,
--CH.sub.2--CH(OH)--(C.sub.1-C.sub.5)alkylene-O--(C.sub.1-C.sub.10)alkyle-
ne-Si(O--(C.sub.1-C.sub.10)alkyl).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2,
[0228] at each occurrence, R.sup.2 is independently selected from
the group consisting of --H,
--CH.sub.2--CH(OH)--(C.sub.1-C.sub.5)alkylene-O--(C.sub.1-C.sub.10)alkyle-
ne-Si(O--(C.sub.1-C.sub.10)alkyl).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2,
[0229] at each occurrence, R.sup.3 is independently selected from
the group consisting of --H,
--CH.sub.2--CH(OH)--(C.sub.1-C.sub.5)alkylene-O--(C.sub.1-C.sub.10)alkyle-
ne-Si(O--(C.sub.1-C.sub.10)alkyl).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2,
[0230] at each occurrence, R.sup.4 is independently selected from
the group consisting of --H and
--CH.sub.2--CH(OH)--(C.sub.1-C.sub.5)alkylene-O--(C.sub.1-C.sub.10)alkyle-
ne-Si(O--(C.sub.1-C.sub.10)alkyl).sub.3,
[0231] at one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 in the silane-functionalized
PEI clay stabilizer molecule is a silicon-containing group,
[0232] at each occurrence, each (C.sub.1-C.sub.10)alkylene,
(C.sub.1-C.sub.8)alkylene, and (C.sub.1-C.sub.10)alkyl is
independently selected,
[0233] n is about 2 to about 1,000,000, and
[0234] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0235] Embodiment 44 provides the method of any one of Embodiments
1-43, wherein the silane-functionalized PAI clay stabilizer has the
structure:
##STR00027##
[0236] wherein
[0237] at each occurrence, R.sup.1 is independently selected from
the group consisting of --H,
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).sub.3,
and --CH.sub.2--CH.sub.2--N(R.sup.2).sub.2,
[0238] at each occurrence, R.sup.2 is independently selected from
the group consisting of --H,
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).sub.3,
and --CH.sub.2--CH.sub.2--N(R.sup.3).sub.2,
[0239] at each occurrence, R.sup.3 is independently selected from
the group consisting of --H,
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).sub.3,
and --CH.sub.2--CH.sub.2--N(R.sup.2).sub.2,
[0240] at each occurrence, R.sup.4 is independently selected from
the group consisting of --H and
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2).sub.3--Si(OCH.sub.3).sub.3,
[0241] at one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 in the silane-functionalized
PEI clay stabilizer molecule is a silicon-containing group,
[0242] n is about 2 to about 1,000,000, and
[0243] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0244] Embodiment 45 provides the method of any one of Embodiments
2-44, wherein the composition further comprises a secondary clay
stabilizer.
[0245] Embodiment 46 provides the method of Embodiment 45, wherein
the secondary clay stabilizer is potassium chloride, a
non-polymeric ionic liquid, an inorganic phosphate, a polyalkoxy
diamine or a salt thereof, choline or a choline derivative, an
oligomethylene diamine or a salt thereof, an addition product of
carboxymethyl cellulose and an organic amine,
1,2-cyclohexanediamine or a salt thereof, a salt of a phosphoric
acid ester of an oxyalkylated polyol, a combination of a partially
hydrolyzed acrylic copolymer potassium chloride and polyanionic
cellulose, a quaternary ammonium compound, a polymer based on
dialkyl aminoalkyl methacrylate, an aqueous solution containing a
polymer with hydrophilic and hydrophobic groups, a reaction product
of a polyhydroxyalkane and an alkylene oxide, or a combination
thereof.
[0246] Embodiment 47 provides the method of any one of Embodiments
2-46, wherein the clay stabilizer composition further comprises
water, saline, aqueous base, oil, organic solvent, synthetic fluid
oil phase, aqueous solution, alcohol or polyol, cellulose, starch,
alkalinity control agent, acidity control agent, density control
agent, density modifier, emulsifier, dispersant, polymeric
stabilizer, polyacrylamide, polymer or combination of polymers,
antioxidant, heat stabilizer, foam control agent, solvent, diluent,
plasticizer, filler or inorganic particle, pigment, dye,
precipitating agent, oil-wetting agent, set retarding additive,
surfactant, corrosion inhibitor, gas, weight reducing additive,
heavy-weight additive, lost circulation material, filtration
control additive, salt, fiber, thixotropic additive, breaker,
crosslinker, gas, rheology modifier, curing accelerator, curing
retarder, pH modifier, chelating agent, scale inhibitor, enzyme,
resin, water control material, polymer, oxidizer, a marker,
Portland cement, pozzolana cement, gypsum cement, high alumina
content cement, slag cement, silica cement, fly ash, metakaolin,
shale, zeolite, a crystalline silica compound, amorphous silica,
fibers, a hydratable clay, microspheres, pozzolan lime, or a
combination thereof.
[0247] Embodiment 48 provides the method of any one of Embodiments
2-47, wherein the placing of the clay stabilizer composition in the
subterranean formation comprises fracturing at least part of the
subterranean formation to form at least one subterranean
fracture.
[0248] Embodiment 49 provides the method of any one of Embodiments
2-48, wherein the clay stabilizer composition further comprises a
proppant, a resin-coated proppant, or a combination thereof.
[0249] Embodiment 50 provides the method of any one of Embodiments
2-49, wherein the placing of the clay stabilizer composition in the
subterranean formation comprises pumping the composition through a
tubular disposed in a wellbore and into the subterranean
formation.
[0250] Embodiment 51 provides the method of any one of Embodiments
2-50, wherein the placing of the clay stabilizer composition in the
subterranean formation comprises pumping the composition through a
drill string disposed in a wellbore, through a drill bit at a
downhole end of the drill string, and back above-surface through an
annulus.
[0251] Embodiment 52 provides the method of Embodiment 51, further
comprising processing the composition exiting the annulus with at
least one fluid processing unit to generate a cleaned composition
and recirculating the cleaned composition through the wellbore.
[0252] Embodiment 53 provides a system for performing the method of
any one of Embodiments 2-52, the system comprising:
[0253] a tubular disposed in the subterranean formation; and
[0254] a pump configured to pump the clay stabilizer composition in
the subterranean formation through the tubular.
[0255] Embodiment 54 provides a system for performing the method of
any one of Embodiments 2-53, the system comprising:
[0256] a drill string disposed in a wellbore, the drill string
comprising a drill bit at a downhole end of the drill string;
[0257] an annulus between the drill string and the wellbore;
and
[0258] a pump configured to circulate the clay stabilizer
composition through the drill string, through the drill bit, and
back above-surface through the annulus.
[0259] Embodiment 55 provides a method of treating a subterranean
formation, the method comprising:
[0260] placing in the subterranean formation a
silane-functionalized polyalkyleneimine (PAI) clay stabilizer,
wherein the silane-functionalized PAI clay stabilizer is a polymer
comprising a repeating unit having the following structure:
##STR00028##
[0261] wherein
[0262] at each occurrence of R.sup.1 and D in the same repeating
unit, [0263] R.sup.1 is independently selected from the group
consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and D is H, or [0264]
R.sup.1 and D together in the same repeating unit form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.1 is
bound,
[0265] at each occurrence, X is independently selected from the
group consisting of --(CH.sub.2).sub.2--O--,
--(CH.sub.2).sub.3--O--, --(CH.sub.2).sub.2--S--,
--(CH.sub.2).sub.3--S--, and a --(C.sub.1-10)alkylene-,
[0266] at each occurrence, m is about 0 to about 10,
[0267] at each occurrence, L.sup.1 is a substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbylene interrupted by 0, 1,
2, or 3 groups independently selected from --O--, --S--, and
substituted or unsubstituted --NH--,
[0268] at each occurrence, R.sup.A is independently selected from
--O--R.sup.B, --H, and --R.sup.B, wherein at least one R.sup.A of
each --Si--(R.sup.A).sub.3 is --O--R.sup.B,
[0269] at each occurrence, R.sup.B is independently substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbyl,
[0270] at each occurrence of R.sup.2 and E in the same R.sup.1 or
in the same R.sup.3, [0271] R.sup.2 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHF--N(R.sup.3).sub.2, and E is H, or [0272]
R.sup.2 and E together in the same R.sup.1 or in the same R.sup.3
form a (C.sub.1-C.sub.10)heterocycle with the N to which R.sup.2 is
bound,
[0273] at each occurrence of R.sup.3 and F in the same R.sup.2,
[0274] R.sup.3 is independently selected from the group consisting
of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and F is H, or [0275]
R.sup.3 and F together in the same R.sup.2 form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.3 is
bound,
[0276] at one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, and R.sup.3 in the silane-functionalized PAI clay
stabilizer molecule is a silicon-containing group, and
[0277] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0278] Embodiment 56 provides a method of treating a subterranean
formation, the method comprising:
[0279] placing in the subterranean formation a
silane-functionalized polyethyleneimine (PEI) clay stabilizer,
wherein the silane-functionalized PEI clay stabilizer is a polymer
comprising a repeating unit having the following structure:
##STR00029##
[0280] wherein
[0281] at each occurrence, R.sup.1 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2,
[0282] at each occurrence, L.sup.1 is a substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbylene interrupted by 0, 1,
2, or 3 groups independently selected from --O--, --S--, and
substituted or unsubstituted --NH--,
[0283] at each occurrence, R.sup.A is independently selected from
--O--R.sup.B, --H, and --R.sup.B, wherein at least one R.sup.A of
each --Si--(R.sup.A).sub.3 is --O--R.sup.B,
[0284] at each occurrence, R.sup.B is independently substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbyl,
[0285] at each occurrence, R.sup.2 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2,
[0286] at each occurrence, R.sup.3 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, and
[0287] at one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, and R.sup.3 in the silane-functionalized PEI clay
stabilizer molecule is a silicon-containing group,
[0288] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0289] Embodiment 57 provides a system comprising:
[0290] a tubular disposed in a subterranean formation; and
[0291] a pump configured to pump a clay stabilizer composition
comprising a silane-functionalized polyalkyleneimine (PAI) clay
stabilizer in the subterranean formation through the tubular.
[0292] Embodiment 58 provides the system of Embodiment 57,
[0293] wherein the tubular comprises a drill string disposed in a
wellbore, the drill string comprising a drill bit at a downhole end
of the drill string; and
[0294] the system comprises an annulus between the drill string and
the wellbore;
[0295] wherein the pump is configured to circulate the clay
stabilizer composition through the drill string, through the drill
bit, and back above-surface through the annulus.
[0296] Embodiment 59 provides the system of any one of Embodiments
57-58, further comprising a fluid processing unit configured to
process the composition exiting the annulus to generate a cleaned
drilling fluid for recirculation through the wellbore.
[0297] Embodiment 60 provides a silane-functionalized
polyalkyleneimine (PAI) clay stabilizer for treatment of a
subterranean formation.
[0298] Embodiment 61 provides a silane-functionalized
polyalkyleneimine (PAI) clay stabilizer for treatment of a
subterranean formation, wherein the silane-functionalized PAI clay
stabilizer is a polymer comprising a repeating unit having the
following structure:
##STR00030##
[0299] wherein
[0300] at each occurrence of R.sup.1 and D in the same repeating
unit, [0301] R.sup.1 is independently selected from the group
consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and D is H, or [0302]
R.sup.1 and D together in the same repeating unit form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.1 is
bound,
[0303] at each occurrence, X is independently selected from the
group consisting of --(CH.sub.2).sub.2--O--,
--(CH.sub.2).sub.3--O--, --(CH.sub.2).sub.2--S--,
--(CH.sub.2).sub.3--S--, and a --(C.sub.1-10)alkylene-,
[0304] at each occurrence, m is about 0 to about 10,
[0305] at each occurrence, L.sup.1 is a substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbylene interrupted by 0, 1,
2, or 3 groups independently selected from --O--, --S--, and
substituted or unsubstituted --NH--,
[0306] at each occurrence, R.sup.A is independently selected from
--O--R.sup.B, --H, and --R.sup.B, wherein at least one R.sup.A of
each --Si--(R.sup.A).sub.3 is --O--R.sup.B,
[0307] at each occurrence, R.sup.B is independently substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbyl,
[0308] at each occurrence of R.sup.2 and E in the same R.sup.1 or
in the same R.sup.3, [0309] R.sup.2 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHF--N(R.sup.3).sub.2, and E is H, or [0310]
R.sup.2 and E together in the same R.sup.1 or in the same R.sup.3
form a (C.sub.1-C.sub.10)heterocycle with the N to which R.sup.2 is
bound,
[0311] at each occurrence of R.sup.3 and F in the same R.sup.2
[0312] R.sup.3 is independently selected from the group consisting
of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and F is H, or [0313]
R.sup.3 and F together in the same R.sup.2 form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.3 is
bound,
[0314] at one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, and R.sup.3 in the silane-functionalized PAI clay
stabilizer molecule is a silicon-containing group, and
[0315] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0316] Embodiment 62 provides a composition comprising the clay
stabilizer of Embodiment 61.
[0317] Embodiment 63 provides a silane-functionalized
polyethyleneimine (PEI) clay stabilizer for treatment of a
subterranean formation.
[0318] Embodiment 64 provides a silane-functionalized
polyethyleneimine (PEI) clay stabilizer for treatment of a
subterranean formation, wherein the silane-functionalized PEI clay
stabilizer is a polymer comprising a repeating unit having the
following structure:
##STR00031##
[0319] wherein
[0320] at each occurrence, R.sup.1 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2,
[0321] at each occurrence, L.sup.1 is a substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbylene interrupted by 0, 1,
2, or 3 groups independently selected from --O--, --S--, and
substituted or unsubstituted --NH--,
[0322] at each occurrence, R.sup.A is independently selected from
--O--R.sup.B, --H, and --R.sup.B, wherein at least one R.sup.A of
each --Si--(R.sup.A).sub.3 is --O--R.sup.B,
[0323] at each occurrence, R.sup.B is independently substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbyl,
[0324] at each occurrence, R.sup.2 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2,
[0325] at each occurrence, R.sup.3 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2,
[0326] at one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, and R.sup.3 in the silane-functionalized clay
stabilizer PEI molecule is a silicon-containing group, and
[0327] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0328] Embodiment 65 provides a composition comprising the clay
stabilizer of Embodiment 64.
[0329] Embodiment 66 provides a silane-functionalized
polyethyleneimine (PEI) clay stabilizer for treatment of a
subterranean formation, wherein the silane-functionalized PEI clay
stabilizer has the structure:
##STR00032##
[0330] wherein
[0331] at each occurrence, R.sup.1 is independently selected from
the group consisting of --H,
--CH.sub.2--CH(OH)--(C.sub.1-C.sub.5)alkylene-O--(C.sub.1-C.sub.10)alkyle-
ne-Si(O--(C.sub.1-C.sub.10)alkyl).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, wherein at each occurrence,
each (C.sub.1-C.sub.10)alkylene, (C.sub.1-C.sub.5)alkylene, and
(C.sub.1-C.sub.10)alkyl is independently selected,
[0332] at each occurrence, R.sup.2 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2,
[0333] at each occurrence, R.sup.3 is independently selected from
the group consisting of --H, -L.sup.1-Si--(R.sup.A).sub.3, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2,
[0334] at each occurrence, R.sup.4 is independently selected from
the group consisting of --H and -L.sup.1-Si--(R.sup.A).sub.3,
[0335] at one or more occurrences, at least one group selected from
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 in the silane-functionalized
clay stabilizer PEI molecule is a silicon-containing group,
[0336] n is about 2 to about 1,000,000, and
[0337] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0338] Embodiment 67 provides a composition comprising the clay
stabilizer of Embodiment 66.
[0339] Embodiment 68 provides a method of preparing a
silane-functionalized polyalkyleneimine (PAI) clay stabilizer for
treatment of a subterranean formation, the method comprising:
[0340] forming a mixture comprising a silane-functionalized epoxide
and a PAI; and
[0341] allowing the mixture to react to form the
silane-functionalized PAI clay stabilizer.
[0342] Embodiment 69 provides the method of Embodiment 68, further
comprising forming a clay stabilizer composition comprising the
silane-functionalized PAI clay stabilizer.
[0343] Embodiment 70 provides the method of any one of Embodiments
68-69, wherein the PAI is a polymer comprising a repeating unit
having the structure:
##STR00033##
[0344] wherein
[0345] at each occurrence of R.sup.1 and D in the same repeating
unit, [0346] R.sup.1 is independently selected from the group
consisting of --H and --(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2,
and D is H, or [0347] R.sup.1 and D together in the same repeating
unit form a (C.sub.1-C.sub.10)heterocycle with the N to which
R.sup.1 is bound,
[0348] at each occurrence, X is independently selected from the
group consisting of --(CH.sub.2).sub.2--O--,
--(CH.sub.2).sub.3--O--, --(CH.sub.2).sub.2--S--,
--(CH.sub.2).sub.3--S--, and a --(C.sub.1-10)alkylene-,
[0349] at each occurrence, m is about 0 to about 10,
[0350] at each occurrence of R.sup.2 and E in the same R.sup.1 or
in the same R.sup.3, [0351] R.sup.2 is independently selected from
the group consisting of --H and
--(X).sub.m--CH.sub.2--CHF--N(R.sup.3).sub.2, and E is H, or [0352]
R.sup.2 and E together in the same R.sup.1 or in the same R.sup.3
form a (C.sub.1-C.sub.10)heterocycle with the N to which R.sup.2 is
bound,
[0353] at each occurrence of R.sup.3 and F in the same R.sup.2,
[0354] R.sup.3 is independently selected from the group consisting
of --H and --(X).sub.m--CH.sub.2--CHE-N(R.sup.2).sub.2, and F is H,
or [0355] R.sup.3 and F together in the same R.sup.2 form a
(C.sub.1-C.sub.10)heterocycle with the N to which R.sup.3 is bound,
and
[0356] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0357] Embodiment 71 provides the method of Embodiment 70, wherein
the PAI is PEI, wherein m is 0, D, E, and F are H, wherein the PAI
is a polymer comprising a repeating unit having the structure:
##STR00034##
[0358] wherein
[0359] at each occurrence, R.sup.1 is independently selected from
the group consisting of --H and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2,
[0360] at each occurrence, R.sup.2 is independently selected from
the group consisting of --H, and
--CH.sub.2--CH.sub.2--N(R.sup.3).sub.2,
[0361] at each occurrence, R.sup.3 is independently selected from
the group consisting of --H, and
--CH.sub.2--CH.sub.2--N(R.sup.2).sub.2, and
[0362] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0363] Embodiment 72 provides the method of Embodiment 71, wherein
the PEI has the structure:
##STR00035##
[0364] wherein
[0365] n is about 2 to about 1,000,000, and
[0366] each amine group is independently in the form of a neutral
amine or a protonated cationic amine.
[0367] Embodiment 73 provides the method of Embodiment 72, wherein
n is about 2 to about 1,000.
[0368] Embodiment 74 provides the method of any one of Embodiments
72-73, wherein n is about 2 to about 100.
[0369] Embodiment 75 provides the method of any one of Embodiments
68-74, wherein the silane-functionalized epoxide has the
structure:
##STR00036##
[0370] wherein
[0371] at each occurrence, L.sup.1A is a substituted or
unsubstituted (C.sub.1-C.sub.20)alkylene interrupted by --O--,
[0372] at each occurrence, R.sup.A is independently selected from
--O--R.sup.B, --H, and --R.sup.B, wherein at least one R.sup.A of
each --Si--(R.sup.A).sub.3 is --O--R.sup.B, and
[0373] at each occurrence, R.sup.B is independently substituted or
unsubstituted (C.sub.1-C.sub.20)hydrocarbyl.
[0374] Embodiment 76 provides the method of Embodiment 75, wherein
at each occurrence, L.sup.1A independently has the structure
-L.sup.2A-O-L.sup.3A-.
[0375] Embodiment 77 provides the method of Embodiment 76, wherein
at each occurrence, L.sup.2A is independently substituted or
unsubstituted (C.sub.1-C.sub.10)alkylene.
[0376] Embodiment 78 provides the method of any one of Embodiments
76-77, wherein at each occurrence, L.sup.2A is independently
unsubstituted (C.sub.1-C.sub.5)alkylene.
[0377] Embodiment 79 provides the method of any one of Embodiments
76-78, wherein at each occurrence, L.sup.3A is independently a
substituted or unsubstituted (C.sub.1-C.sub.10)alkylene.
[0378] Embodiment 80 provides the method of any one of Embodiments
76-79, wherein L.sup.3A is --CH.sub.2--.
[0379] Embodiment 81 provides the method of any one of Embodiments
76-80, wherein L.sup.1A is:
##STR00037##
[0380] Embodiment 82 provides the method of any one of Embodiments
75-81, wherein R.sup.A is --O--R.sup.B.
[0381] Embodiment 83 provides the method of any one of Embodiments
75-82, wherein at each occurrence, R.sup.B is independently
(C.sub.1-C.sub.20)alkyl.
[0382] Embodiment 84 provides the method of any one of Embodiments
75-83, wherein at each occurrence, R.sup.B is independently
(C.sub.1-C.sub.5)alkyl.
[0383] Embodiment 85 provides the method of any one of Embodiments
75-84, wherein R.sup.B is methyl.
[0384] Embodiment 86 provides the method of any one of Embodiments
68-85, wherein the silane-functionalized epoxide has the
structure:
##STR00038##
[0385] Embodiment 87 provides the method of any one of Embodiments
68-86, wherein the molar ratio of the silane-functionalized epoxide
to the PEI is about 1:100,000 to about 100:1.
[0386] Embodiment 88 provides the method of any one of Embodiments
68-87, wherein the molar ratio of the silane-functionalized epoxide
to the PEI is about 2:1 to about 6:1.
[0387] Embodiment 89 provides the method of any one of Embodiments
68-88, wherein the pH of the mixture is about 7 to about 12.
[0388] Embodiment 90 provides the method of any one of Embodiments
68-89, wherein the pH of the mixture is about 8 to about 10.
[0389] Embodiment 91 provides the method, system, or composition of
any one or any combination of Embodiments 1-90 optionally
configured such that all elements or options recited are available
to use or select from.
* * * * *