U.S. patent application number 13/914513 was filed with the patent office on 2013-10-17 for aggregating compositions, modified particulate metal-oxides, modified formation surfaces, and methods for making and using same.
The applicant listed for this patent is CLEARWATER INTERNATIONAL, LLC. Invention is credited to Erin Fitzgerald, Tina Garza, Sarkis R. Kakadjian, Raynard Veldman, Frank Zamora.
Application Number | 20130270012 13/914513 |
Document ID | / |
Family ID | 42313696 |
Filed Date | 2013-10-17 |
United States Patent
Application |
20130270012 |
Kind Code |
A1 |
Kakadjian; Sarkis R. ; et
al. |
October 17, 2013 |
AGGREGATING COMPOSITIONS, MODIFIED PARTICULATE METAL-OXIDES,
MODIFIED FORMATION SURFACES, AND METHODS FOR MAKING AND USING
SAME
Abstract
A method for treating solid materials is disclosed, where the
treating compositions coats surfaces or portions of surfaces of the
solid materials changing an aggregation or agglomeration propensity
of the materials. Treating composition and treated solid materials
are also disclosed. The methods and treated materials are ideally
suited for oil field applications.
Inventors: |
Kakadjian; Sarkis R.;
(Houston, TX) ; Veldman; Raynard; (Houston,
TX) ; Zamora; Frank; (Houston, TX) ;
Fitzgerald; Erin; (San Antonio, TX) ; Garza;
Tina; (San Antonio, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CLEARWATER INTERNATIONAL, LLC |
Houston |
TX |
US |
|
|
Family ID: |
42313696 |
Appl. No.: |
13/914513 |
Filed: |
June 10, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12465437 |
May 13, 2009 |
8466094 |
|
|
13914513 |
|
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Current U.S.
Class: |
175/65 |
Current CPC
Class: |
C09K 8/5751 20130101;
E21B 21/00 20130101; C09K 8/035 20130101; C09K 8/80 20130101; C09K
8/805 20130101; C09K 8/88 20130101; C09K 8/68 20130101; E21B 21/085
20200501 |
Class at
Publication: |
175/65 |
International
Class: |
C09K 8/035 20060101
C09K008/035; E21B 21/00 20060101 E21B021/00 |
Claims
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23. (canceled)
24. (canceled)
25. The method of claim 34, wherein a pressure of the drilling
fluid is operated in an over-balanced pressure condition, an
under-balanced pressure condition or a managed pressure
condition.
26. (canceled)
27. (canceled)
28. (canceled)
29. (canceled)
30. (canceled)
31. (canceled)
32. (canceled)
33. (canceled)
34. A method for drilling comprising the step of: while drilling,
circulating a drilling fluid, to provide bit lubrication, heat
removal and cutting removal, where the drilling fluid includes an
aggregating composition including a polymer comprising homopolymers
selected from the group consisting of poly-2-vinyl pyridine,
poly-4-vinyl pyridine, and mixtures or combinations thereof and
copolymers selected from the group consisting of copolymers of
2-vinyl pyridine and 4-vinyl pyridine, copolymers of ethylene and
2-vinyl pyridine and/or 4-vinyl pyridine, copolymers of propylene
and 2-vinyl pyridine and/or 4-vinyl pyridine, copolymers of acrylic
acid and 2-vinyl pyridine and/or 4-vinyl pyridine, copolymers of
methacrylic acid and 2-vinyl pyridine and/or 4-vinyl pyridine,
copolymers of acrylates and 2-vinyl pyridine and/or 4-vinyl
pyridine, copolymers of methacrylates and 2-vinyl pyridine and/or
4-vinyl pyridine, and mixtures or combinations thereof and where
the composition increases an aggregation potential or propensity
and/or alters a zeta potential of any particulate solid in the
drilling fluid or that becomes entrained in the drilling fluid to
increase solids removal.
35. The method of claim 34, further comprising a reaction product
of an amine and a phosphate-containing compound.
36. The method of claim 35, wherein the amine comprises amines
having the general formula R.sup.1,R.sup.2NH or mixtures or
combinations thereof, where R.sup.1 and R.sup.2 are independently a
hydrogen atom or a carbyl group having between about between about
1 and 40 carbon atoms and the required hydrogen atoms to satisfy
the valence and where one or more of the carbon atoms can be
replaced by one or more hetero atoms selected from the group
consisting of boron, nitrogen, oxygen, phosphorus, sulfur or
mixture or combinations thereof and where one or more of the
hydrogen atoms can be replaced by one or more single valence atoms
selected from the group consisting of fluorine, chlorine, bromine,
iodine or mixtures or combinations thereof and the
phosphate-containing compound comprises phosphate acids and esters
having the general formula P(O)(OR.sup.3)(OR.sup.4)(OR.sup.5) or
mixture or combinations thereof, where R.sup.3, R.sup.4, and
OR.sup.5 are independently a hydrogen atom or a carbyl group having
between about between about 1 and 40 carbon atoms and the required
hydrogen atoms to satisfy the valence and where one or more of the
carbon atoms can be replaced by one or more hetero atoms selected
from the group consisting of boron, nitrogen, oxygen, phosphorus,
sulfur or mixture or combinations thereof and where one or more of
the hydrogen atoms can be replaced by one or more single valence
atoms selected from the group consisting of fluorine, chlorine,
bromine, iodine or mixtures or combinations thereof or polymeric
forms thereof.
37. The method of claim 36, wherein the amine is selected from the
group consisting of aniline and alkyl anilines or mixtures of alkyl
anilines, pyridines and alkyl pyridines or mixtures of alkyl
pyridines, pyrrole and alkyl pyrroles or mixtures of alkyl
pyrroles, piperidine and alkyl piperidines or mixtures of alkyl
piperidines, pyrrolidine and alkyl pyrrolidines or mixtures of
alkyl pyrrolidines, indole and alkyl indoles or mixture of alkyl
indoles, imidazole and alkyl imidazole or mixtures of alkyl
imidazole, quinoline and alkyl quinoline or mixture of alkyl
quinoline, isoquinoline and alkyl isoquinoline or mixture of alkyl
isoquinoline, pyrazine and alkyl pyrazine or mixture of alkyl
pyrazine, quinoxaline and alkyl quinoxaline or mixture of alkyl
quinoxaline, acridine and alkyl acridine or mixture of alkyl
acridine, pyrimidine and alkyl pyrimidine or mixture of alkyl
pyrimidine, quinazoline and alkyl quinazoline or mixture of alkyl
quinazoline, or mixtures or combinations thereof.
38. The method of claim 36, wherein the phosphate-containing
compound comprises phosphate esters of alkanols having the general
formula P(O)(OH).sub.x(OR.sup.6).sub.y where x+y=3 and are
independently a hydrogen atom or a carbyl group having between
about between about 1 and 40 carbon atoms and the required hydrogen
atoms to satisfy the valence and where one or more of the carbon
atoms can be replaced by one or more hetero atoms selected from the
group consisting of boron, nitrogen, oxygen, phosphorus, sulfur or
mixture or combinations thereof and where one or more of the
hydrogen atoms can be replaced by one or more single valence atoms
selected from the group consisting of fluorine, chlorine, bromine,
iodine or mixtures or combinations thereof such as ethoxy
phosphate, propoxyl phosphate or higher alkoxy phosphates or
mixtures or combinations thereof.
39. The method of claim 36, wherein the phosphate-containing
compound comprises phosphate esters of alkanol amines having the
general formula N[R.sup.7OP(O)(OH).sub.2].sub.3 where R.sup.7 is a
carbenzyl group having between about between about 1 and 40 carbon
atoms and the required hydrogen atoms to satisfy the valence and
where one or more of the carbon atoms can be replaced by one or
more hetero atoms selected from the group consisting of boron,
nitrogen, oxygen, phosphorus, sulfur or mixture or combinations
thereof and where one or more of the hydrogen atoms can be replaced
by one or more single valence atoms selected from the group
consisting of fluorine, chlorine, bromine, iodine or mixtures or
combinations thereof group including the tri-phosphate ester of
tri-ethanol amine or mixtures or combinations thereof.
40. A method for drilling comprising the step of: while drilling,
circulating a first drilling fluid, to provide bit lubrication,
heat removal and cutting removal, upon encountering an underground
structure that produces undesirable quantities of particulate
solids, changing the first drilling fluid to a second drilling
fluid including an aggregating composition comprising a polymer
comprising homopolymers selected from the group consisting of
poly-2-vinyl pyridine, poly-4-vinyl pyridine, and mixtures or
combinations thereof and copolymers selected from the group
consisting of copolymers of 2-vinyl pyridine and 4-vinyl pyridine,
copolymers of ethylene and 2-vinyl pyridine and/or 4-vinyl
pyridine, copolymers of propylene and 2-vinyl pyridine and/or
4-vinyl pyridine, copolymers of acrylic acid and 2-vinyl pyridine
and/or 4-vinyl pyridine, copolymers of methacrylic acid and 2-vinyl
pyridine and/or 4-vinyl pyridine, copolymers of acrylates and
2-vinyl pyridine and/or 4-vinyl pyridine, copolymers of
methacrylates and 2-vinyl pyridine and/or 4-vinyl pyridine, and
mixtures or combinations thereof to provide bit lubrication, heat
removal and cutting removal and to increase an aggregation
potential or decrease the absolute value of a zeta potential of any
particulate solids in the drilling fluid or that becomes entrained
in the drilling fluid to increase solids removal.
41. The method of claim 40, further comprising the step of: after
passing through the structure that produces an undesired quantities
of particulate solids, changing the second drilling fluid to the
first drilling fluid or to a third drilling fluid.
42. The method of claim 41, wherein a pressure of the first
drilling fluid, the second drilling fluid and the third drilling
fluid are operated in an over-balanced pressure condition, an
under-balanced pressure condition, or a managed pressure
condition.
43. The method of claim 40, wherein the second drilling fluid
further comprising a reaction product of an amine and a
phosphate-containing compound.
44. The method of claim 43, wherein the amine comprises amines
having the general formula R.sup.1,R.sup.2NH or mixtures or
combinations thereof, where R.sup.1 and R.sup.2 are independently a
hydrogen atom or a carbyl group having between about between about
1 and 40 carbon atoms and the required hydrogen atoms to satisfy
the valence and where one or more of the carbon atoms can be
replaced by one or more hetero atoms selected from the group
consisting of boron, nitrogen, oxygen, phosphorus, sulfur or
mixture or combinations thereof and where one or more of the
hydrogen atoms can be replaced by one or more single valence atoms
selected from the group consisting of fluorine, chlorine, bromine,
iodine or mixtures or combinations thereof and the
phosphate-containing compound comprises phosphate acids and esters
having the general formula P(O)(OR.sup.3)(OR.sup.4)(OR.sup.5) or
mixture or combinations thereof, where R.sup.3, R.sup.4, and
OR.sup.5 are independently a hydrogen atom or a carbyl group having
between about between about 1 and 40 carbon atoms and the required
hydrogen atoms to satisfy the valence and where one or more of the
carbon atoms can be replaced by one or more hetero atoms selected
from the group consisting of boron, nitrogen, oxygen, phosphorus,
sulfur or mixture or combinations thereof and where one or more of
the hydrogen atoms can be replaced by one or more single valence
atoms selected from the group consisting of fluorine, chlorine,
bromine, iodine or mixtures or combinations thereof or polymeric
forms thereof.
45. The method of claim 44, wherein the amine is selected from the
group consisting of aniline and alkyl anilines or mixtures of alkyl
anilines, pyridines and alkyl pyridines or mixtures of alkyl
pyridines, pyrrole and alkyl pyrroles or mixtures of alkyl
pyrroles, piperidine and alkyl piperidines or mixtures of alkyl
piperidines, pyrrolidine and alkyl pyrrolidines or mixtures of
alkyl pyrrolidines, indole and alkyl indoles or mixture of alkyl
indoles, imidazole and alkyl imidazole or mixtures of alkyl
imidazole, quinoline and alkyl quinoline or mixture of alkyl
quinoline, isoquinoline and alkyl isoquinoline or mixture of alkyl
isoquinoline, pyrazine and alkyl pyrazine or mixture of alkyl
pyrazine, quinoxaline and alkyl quinoxaline or mixture of alkyl
quinoxaline, acridine and alkyl acridine or mixture of alkyl
acridine, pyrimidine and alkyl pyrimidine or mixture of alkyl
pyrimidine, quinazoline and alkyl quinazoline or mixture of alkyl
quinazoline, or mixtures or combinations thereof.
46. The method of claim 44, wherein the phosphate-containing
compound comprises phosphate esters of alkanols having the general
formula P(O)(OH)(OR.sup.6).sub.y where x+y=3 and are independently
a hydrogen atom or a carbyl group having between about between
about 1 and 40 carbon atoms and the required hydrogen atoms to
satisfy the valence and where one or more of the carbon atoms can
be replaced by one or more hetero atoms selected from the group
consisting of boron, nitrogen, oxygen, phosphorus, sulfur or
mixture or combinations thereof and where one or more of the
hydrogen atoms can be replaced by one or more single valence atoms
selected from the group consisting of fluorine, chlorine, bromine,
iodine or mixtures or combinations thereof such as ethoxy
phosphate, propoxyl phosphate or higher alkoxy phosphates or
mixtures or combinations thereof.
47. The method of claim 44, wherein the phosphate-containing
compound comprises phosphate esters of alkanol amines having the
general formula N[R.sup.7OP(O)(OH).sub.2].sub.3 where R.sup.7 is a
carbenzyl group having between about between about 1 and 40 carbon
atoms and the required hydrogen atoms to satisfy the valence and
where one or more of the carbon atoms can be replaced by one or
more hetero atoms selected from the group consisting of boron,
nitrogen, oxygen, phosphorus, sulfur or mixture or combinations
thereof and where one or more of the hydrogen atoms can be replaced
by one or more single valence atoms selected from the group
consisting of fluorine, chlorine, bromine, iodine or mixtures or
combinations thereof group including the tri-phosphate ester of
tri-ethanol amine or mixtures or combinations thereof.
Description
RELATED APPLICATIONS
[0001] This application claims the benefit of and priority to U.S.
patent application Ser. No. 12/465,437, filed 13 May 2009 (May 13,
2009), now U.S. Pat. No. 8,466,094, issued 18 Jun. 2013 (Jun. 18,
2013).
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] Embodiments of the present invention relate to compositions
including aggregating agents for solid materials, substrates or
surfaces, where the materials, substrates or surfaces include metal
oxide or ceramic solid materials, substrates or surfaces (natural
or synthetic), metallic solid materials, substrates or surfaces,
polymeric or plastic solid materials, substrates or surfaces
(natural or synthetic), solid plant materials, substrates or
surfaces (natural or treated), or other types of solid materials,
substrates or surfaces or formation surfaces, formation
particulate, and formation fines and methods for making and using
same.
[0004] More particularly, the present invention relate to
compositions including aggregating agents for particulate solid
materials or substrates, where the aggregating agents modify
surface properties of solid surfaces and surfaces of particulate
solid materials increasing their aggregating propensity or
properties. The present invention also relates to coated or
modified surfaces and/or particulate solid materials capable of
self-aggregation or aggregating to a coated surface. The present
invention also relates to methods for aggregating particulate solid
materials and for aggregating particulate solid materials to
treated solid surfaces, especially in downhole applications and in
any other application where particulate metal oxide-containing
solids aggregation is desirable. Embodiments of the present
invention are ideally suitable for drilling, completion, fracturing
or other oil/gas well operations, where particulate control is
needed, enhanced production, reduced flow back, reduced water block
in, enhanced load recovery, and changes in zeta potential or
aggregation propensity of particulate.
[0005] 2. Description of the Related Art
[0006] Historically the use of tacky-sticky materials within a
particulate laden fluid whereby particulate flowback is reduced or
prevented is dated back to 1998. U.S. Pat. No. 5,787,986 assignee
to Halliburton shows mainly how the use of polyamides product
mainly from the condensation of polyamines and di-acids is capable
of decrease of substantially eliminates the flowback of
particulates whether proppant or formation fines. U.S. Pat. No.
7,392,847 granted to Weatherford shows that the product of the
reaction between a primary amine and a phosphate ester is capable
of change the aggregation or agglomeration propensity of the
materials.
[0007] In many situations, sand, particulate metal oxide-containing
solids or other particulate materials or solid materials are
difficult to consolidate in underground formations once placed due
to their inability to aggregate or to cling to each other or to
form aggregated masses that allow formation fluid flow back through
the placed or pumped-in fluids without flowing solids back to the
surface. In addition, other situations occur where formation sand
flows due to formation unconsolidated characteristics, and the
flowing sand is transported to the surface during well
production.
[0008] Although several technologies now exist for tackifying such
particulate solid with a tackifying agent, there is a need in the
art of a different treating composition to cause such particulate
solids to self-aggregate and to methods for making self-aggregating
particulate solids.
SUMMARY OF THE INVENTION
Compositions
[0009] The present invention provides a particulate solid material
such as a metal oxide-containing solid having improved
self-aggregating properties. The improved self-aggregating or
aggregation propensity of the particles derives from the surfaces
of the particulate solids having a coating including a polymer
including repeat units derived from vinyl monomers including a
cyclic or aromatic nitrogen-containing ring or ring system or a
polymer having repeat units derived from a heterocyclic or
heterocyclic aromatic vinyl monomer, where the hetero atom is a
nitrogen atom or a nitrogen atom and another hetero atoms selected
from the group consisting of a boron atom, an oxygen atom, a
phosphorus atom, a sulfur atom, and/or a germanium and optionally a
reaction product of an amine and a phosphate-containing compound.
The coating can also include a reaction product of an amine and a
phosphate containing compound.
[0010] The present invention provides particulate solid material
such as a metal oxide-containing solids having a coating including
a polymer including repeat units derived from vinyl monomers
including a cyclic or aromatic nitrogen-containing ring or ring
system and optionally a reaction product of an amine and a
phosphate containing compound, where the coating deforms under
pressure and imparts an enhanced aggregating propensity to the
solid particles.
[0011] The present invention provides an aggregated particulate
solid material such as metal oxide-containing solid composition
including a particulate metal oxide-containing solid coated with a
polymer having repeat units derived from a heterocyclic or
heterocyclic aromatic vinyl monomer, where the hetero atom is a
nitrogen atom or a nitrogen atom and another hetero atoms selected
from the group consisting of a boron atom, an oxygen atom, a
phosphorus atom, a sulfur atom, and/or a germanium and optionally a
reaction product of an amine and a phosphate-containing compound,
where the coating is deformable.
[0012] The present invention provides a substrate having surfaces
partially or completed coated with a composition of this invention
comprising a polymer having repeat units derived from a
heterocyclic or heterocyclic aromatic vinyl monomer, where the
hetero atom is a nitrogen atom or a nitrogen atom and another
hetero atoms selected from the group consisting of a boron atom, an
oxygen atom, a phosphorus atom, a sulfur atom, and/or a germanium
and optionally a reaction product of an amine and a
phosphate-containing compound, where the coating is deformable and
where the substrate is ideally suited for filtering fines and/or
other particulate materials form a fluid, especially fluids used in
oil/gas well drilling, completion, production, fracturing,
propping, other production enhancing processes or other related
applications. The structures can be ceramic or ceramic fibers or
wools coated partially or completely with the compositions of this
invention. Such structures are well suited for filter media to be
used with or without screens.
Method for Treating
[0013] The present invention provides a method for changing an
aggregation potential or propensity of a particulate solid material
such as a metal oxide-containing solid, where the method includes
the step of contacting the particulate solid material with a
composition including a polymer having repeat units derived from a
heterocyclic or heterocyclic aromatic vinyl monomer, where the
hetero atom is a nitrogen atom or a nitrogen atom and another
hetero atoms selected from the group consisting of a boron atom, an
oxygen atom, a phosphorus atom, a sulfur atom, and/or a germanium
and optionally a reaction product of an amine and a
phosphate-containing compound under conditions sufficient for the
amine and phosphate containing compound to react forming a coating
composition capable of partially or completely coating solid
surfaces.
Methods for Using the Treating Methods
Fracturing
[0014] The present invention provides a method for fracturing a
formation including the step of pumping a fracturing fluid
including a proppant into a producing formation at a pressure
sufficient to fracture the formation and to enhance productivity,
where the proppant props open the formation after fracturing and
where the proppant comprises a particulate solid treated with a
treating composition comprising a polymer including repeat units
derived from vinyl monomers including a cyclic or aromatic
nitrogen-containing ring or ring system and optionally a reaction
product of an amine and a phosphate containing compound under
conditions sufficient for the amine and phosphate containing
compound to react forming a coating composition capable of
partially or completely coating solid surfaces.
[0015] The present invention provides a method for fracturing a
formation including the step of pumping a fracturing fluid
including a proppant and an aggregating composition of this
invention into a producing formation at a pressure sufficient to
fracture the formation and to enhance productivity. The composition
results in a modification of an aggregation propensity, and/or
zeta-potential of the proppant, formation particles and formation
surfaces so that the formation particles and/or proppant aggregate
and/or cling to the formation surfaces.
[0016] The present invention provides a method for fracturing a
formation including the step of pumping a fracturing fluid
including an aggregating composition of this invention into a
producing formation at a pressure sufficient to fracture the
formation and to enhance productivity. The composition results in a
modification of an aggregation propensity and/or zeta-potential of
the formation particles and formation surfaces so that the
formation particles aggregate and/or cling to the formation
surfaces. The method can also include the step of pumping a
proppant comprising a coated particulate solid composition of this
invention after fracturing so that the coated particles prop open
the fracture formation and tend to aggregate to the formation
surfaces and/or formation particles formed during fracturing.
Drilling
[0017] The present invention provides a method for drilling
including the step of while drilling, circulating a drilling fluid,
to provide bit lubrication, heat removal and cutting removal, where
the drilling fluid includes an aggregating composition of this
invention. The composition increases an aggregation potential or
propensity and/or alters a zeta potential of any particulate metal
oxide-containing solid in the drilling fluid or that becomes
entrained in the drilling fluid to increase solids removal. The
method can be operated in over-pressure conditions or
under-balanced conditions or under managed pressure conditions. The
method is especially well tailored to under-balanced or managed
pressure conditions.
[0018] The present invention provides a method for drilling
including the step of while drilling, circulating a first drilling
fluid to provide bit lubrication, heat removal and cutting removal.
Upon encountering an underground structure that produces
undesirable quantities of particulate solids, changing the first
drilling fluid to a second drilling fluid including a composition
of this invention to provide bit lubrication, heat removal and
cutting removal and to increase an aggregation potential or
decrease the absolute value of the zeta potential of any
particulate solids in the drilling fluid or that becomes entrained
in the drilling fluid to increase solids removal. The method can be
operated in over-pressure conditions or under-balanced conditions
or under managed pressure conditions. The method is especially well
tailored to under-balanced or managed pressure conditions.
[0019] The present invention provides a method for drilling
including the step of while drilling, circulating a first drilling
fluid to provide bit lubrication, heat removal and cutting removal.
Upon encountering an underground structure that produces
undesirable quantities of particulate solids, changing the first
drilling fluid to a second drilling fluid including a composition
of this invention to provide bit lubrication, heat removal and
cutting removal and to increase an aggregation potential or
decrease in the absolute value of the zeta potential of any
particulate solids in the drilling fluid or that becomes entrained
in the drilling fluid to increase solids removal. After passing
through the structure that produces an undesired quantities of
particulate solids, change the second drilling fluid to the first
drilling fluid or a third drilling fluid. The method can be
operated in over-pressure conditions or under-balanced conditions
or under managed pressure conditions. The method is especially well
tailored to under-balanced or managed pressure conditions.
[0020] The present invention provides a method for completion of a
well including the step of treating the well with a fluid including
a composition of this invention adapted to increase an aggregation
potential or decrease in the absolute value of the zeta potential
of particulate solids and fines and formation surfaces resulting in
fine and sand migration and increasing productivity of the well
especially gas productivity.
Producing
[0021] The present invention provides a method for producing
including the step of circulating and/or pumping a fluid into a
well on production, where the fluid includes a composition of this
invention, which increases an aggregation potential or decreases
the absolute value of the zeta potential of any particulate solid
in the fluid or that becomes entrained in the fluid to increase
solid particle removal and to decrease the potential of the
particles to plug the formation and/or the production tubing.
[0022] The present invention also provides a method for controlling
sand or fines migration including the step of pumping a fluid
including a composition of this invention through a matrix at a
rate and pressure into a formation to control sand and fine
production or migration into the production fluids.
[0023] The present invention also provide another method for
controlling sand or fines migration including the step of
depositing a coated particulate solid material of this invention
adjacent screen-type sand and fines control devices so that the
sand and/or fines are attracted to the coated particles and do not
encounter or foul the screen of the screen-type device.
[0024] The aggregating composition of this invention include
polymers including repeat units of cyclic or aromatic amines like
quinoline or alkyl quinoline, anilines or alkyl anilines, pyrrole
or alkyl pyrrole, piperidine or alkyl piperidine, pirrolidine or
alkyl pyrrolidine, Imidazole or alkyl imidazole, pyrazine or alkyl
pyrazine, pyrimidine or alkyl pyrimidine, quinazoline or alkyl
quinazoline.
[0025] Basically the difference of this approach to previous art is
that this is not based in polyamides or quaternized cyclic and
aromatic amines.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] The invention can be better understood with reference to the
following detailed description together with the appended
illustrative drawings in which like elements are numbered the
same:
[0027] FIG. 1 depicts agglomeration properties of 20/40 sand before
treatment and after treatment with a treating fluid including
Formulation 1 at a concentration of 6 gal of Formula 1 per 1000 lb
of sand.
[0028] FIG. 2 depicts a diagram of a liquid permeability apparatus
used in this invention.
[0029] FIG. 3 depicts a diagram of a gas permeability apparatus
used in this invention.
[0030] FIG. 4 depicts a plot of relative permeability versus number
of porous volumes of gas for treating composition.
DETAILED DESCRIPTION OF THE INVENTION
[0031] The inventors have found that a composition can be produced
that, when added to a particulate metal-oxide-containing solid or
other solid materials or to a suspension or dispersion including a
particulate metal-oxide-containing solid or other solid materials,
the particles are modified so that an aggregation propensity,
aggregation potential and/or a zeta potential of the particles are
altered. The inventors have also found that metal-oxide-containing
solid particles or other solid particles can be prepared having
modified surfaces or portions thereof, where the modified particles
have improved aggregation tendencies and/or propensities and/or
alter particle zeta potentials. The inventors have also found that
the compositions and/or the modified metal-oxide-containing solid
or other solid particles can be used in oil field applications
including drilling, fracturing, producing, injecting, sand control,
or any other downhold application. The inventors have also found
that the modified particulate metal-oxide-containing solid
particles or particles of any other solid material can be used any
other application where increased particle aggregation potentials
are desirable or where decreased absolute values of the zeta
potential of the particles, which is a measure of aggregation
propensity. The inventors have also found that a coated particulate
metal-oxide-containing solid compositions can be formed, where the
coating is deformable and the coated particles tend to
self-aggregate and tend to cling to surfaces having similar
coatings or having similar chemical and/or physical properties to
that of the coating. That is to say, that the coated particles tend
to prefer like compositions, which increase their self-aggregation
propensity and increase their ability to adhere to surface that
have similar chemical and/or physical properties. The inventors
have found that the coating compositions of this invention are
distinct from known compositions for modifying particle aggregation
propensities and that the coated particles are ideally suited as
proppants, where the particles have altered zeta potentials that
change the charge on the particles causing them to attract and
agglomerate. The change in zeta potential or aggregation propensity
causes each particle to have an increased frictional drag keeping
the proppant in the fracture. The compositions are also ideally
suited for decreasing fines migrating into a fracture pack or to
decrease the adverse impact of fines migration into a fractured
pack.
[0032] The chemical systems of this invention can be used as
aggregating reagents mainly to control proppant flow back and fine
movement as well as improving gas production and load recovery of
fracture and squeeze jobs.
[0033] In the case of drilling, the compositions of this invention
can be used to coat the formation and formation cuttings during
drilling, because the particle tend to self aggregate and/or cling
to similar modified formation surfaces. Again, an advantage of the
self-aggregation is a reduced tendency of the cuttings to foul or
plug screens. Additional advantages are to coat the formation walls
with a composition of this invention during drilling to consolidate
the formation and to consolidate or aggregate fines or particles in
the drilling fluid to keep the rheological properties of the
drilling fluid from changing and increasing equivalent circulating
density (ECD).
Compositions
[0034] The invention broadly relates to a composition including a
polymer having repeat units derived from a heterocyclic or
heterocyclic aromatic vinyl monomer, where the hetero atom is a
nitrogen atom or a nitrogen atom and another hetero atoms selected
from the group consisting of a boron atom, an oxygen atom, a
phosphorus atom, a sulfur atom, and/or a germanium and optionally a
reaction product of an amine and a phosphate-containing compound.
The composition modifies surfaces of solid materials or portions
thereof altering the chemical and/or physical properties of the
surfaces. The altered properties permit the surfaces to become self
attracting or to permit the surfaces to be attractive to material
having similar chemical and/or physical properties. In the case of
particles including metal oxide particles such as particles of
silica, alumina, titania, magnesia, zirconia, other metal oxides or
oxides including a mixture of these metal oxides (natural or
synthetic), the composition forms a complete or partial coating on
the surfaces of the particles. The coating can interact with the
surface by chemical and/or physical interactions including, without
limitation, chemical bonds, hydrogen bonds, electrostatic
interactions, dipolar interactions, hyperpolarizability
interactions, cohesion, adhesion, adherence, mechanical adhesion or
any other chemical and/or physical interaction that allows a
coating to form on the particles. The coated particles have a
greater aggregation or agglomeration propensity than the uncoated
particles. Thus, the particles before treatment may be free
flowing, while after coating are not free flowing, but tend to
clump, aggregate or agglomerate. In cases, where the composition is
used to coat surfaces of a geological formation, a synthetic metal
oxide structure and/or metal-oxide containing particles, the
particles will not only tend to aggregate together, the particles
also will tend to cling to the coated formation or structural
surfaces.
Treated Structures and Substrates
[0035] The present invention also broadly relates to structures and
substrates treated with a composition of this invention, where the
structures and substrates include surfaces that are partially or
completely coated with a composition of this invention. The
structures or substrates can be ceramic or metallic or fibrous. The
structures or substrates can be spun such as a glass wool or steel
wool or can be honeycombed like catalytic converters or the like
that include channels that force fluid to flow through tortured
paths so that particles in the fluid are forced in contact with the
substrate or structured surfaces. Such structures or substrates are
ideally suited as particulate filters or sand control media.
Methods for Treating Particulate Solids
[0036] The present invention broadly relates to a method for
treating metal oxide-containing surfaces including the step of
contacting the metal oxide-containing surface with a composition of
this invention. The composition forms a coating on the surface
altering the properties of the surface so that the surface is now
capable to interacting with similarly treated surfaces to form
agglomerated and/or aggregated structures. The treating can be
designed to coat continuous metal oxide containing surfaces and/or
the surfaces of metal oxide containing particles. If both are
treated, then the particles cannot only self-aggregate, but the
particles can also aggregate, agglomerate and/or cling to the coted
continuous surfaces. The compositions can be used in fracturing
fluids, in drilling fluids, in completion fluids, in sand control
applications or any other downhole application. Additionally, the
coated particles can be used in fracturing fluids. Moreover,
structures, screens or filters coated with the compositions of this
invention can be used to attract and remove fines that have been
modified with the compositions of this invention.
Method for Fracturing and/or Propping
[0037] The present invention broadly relates to methods for
fracturing a formation including the step of pumping a fracturing
fluid including a composition of this invention into a producing
formation at a pressure sufficient to fracture the formation. The
composition modifies an aggregation potential and/or zeta-potential
of formation particles and formation surfaces during fracturing so
that the formation particles aggregate and/or cling to the
formation surfaces or each other increasing fracturing efficiency
and increasing productivity of the fracture formation. The
composition of this invention can also be used in a pre-pad step to
modify the surfaces of the formation so that during fracturing the
formation surfaces are pre-coated. The prepad step involves pumping
a fluid into the formation ahead of the treatment to initiate the
fracture and to expose the formation face with fluids designed to
protect the formation. Beside just using the composition as part of
the fracturing fluid, the fracturing fluid can also include
particles that have been prior treated with the composition of this
invention, where the treated particles act as proppants to prop
open the formation after fracturing. If the fracturing fluid also
includes the composition, then the coated particle proppant will
adhere to formation surfaces to a greater degree than would
uncoated particle proppant.
[0038] In an alternate embodiment of this invention, the fracturing
fluid includes particles coated with a composition of this
invention as proppant. In this embodiment, the particles have a
greater self-aggregation propensity and will tend to aggregate in
locations that may most need to be propped open. In all fracturing
applications including proppants coated with or that become coated
with the composition of this invention during fracturing, the
coated proppants are likely to have improved formation penetration
and adherence properties. These greater penetration and adherence
or adhesion properties are due not only to a difference in the
surface chemistry of the particles relative to the surface
chemistry of un-treated particles, but also due to a deformability
of the coating itself. Thus, the inventors believe that as the
particles are being forced into the formation, the coating will
deform to allow the particles to penetrate into a position and as
the pressure is removed the particles will tend to remain in place
due to the coating interaction with the surface and due to the
relaxation of the deformed coating.
Method for Drilling
[0039] The present invention also broadly relates to a method for
drilling including the step of, while drilling, circulating a
drilling fluid to provide bit lubrication, heat removal and cutting
removal, where the drill fluid includes a composition of this
invention, which increases an aggregation potential or decrease an
absolute value of the zeta potential of any particulate solids in
the drilling fluid or that becomes entrained in the drilling fluid
to increase solids removal.
[0040] The present invention also broadly relates to a method for
drilling including the step of while drilling, circulating a first
drilling fluid to provide bit lubrication, heat removal and cutting
removal. Upon encountering an underground structure that produces
undesirable quantities of particulate solids including metal
oxide-containing solids, changing the first drilling fluid for a
second drilling fluid including a composition of this invention to
provide bit lubrication, heat removal and cutting removal and to
increase an aggregation potential or decrease an absolute value of
the zeta potential of any solid including particulate metal
oxide-containing solids in the drilling fluid or that becomes
entrained in the drilling fluid to increase solids removal.
[0041] The present invention also broadly relates to a method for
drilling including the step of, while drilling, circulating a first
drilling fluid to provide bit lubrication, heat removal and cutting
removal. Upon encountering an underground structure that produces
undesirable quantities of particulate solids including metal
oxide-containing solids, changing the first drilling fluid for a
second drilling fluid including a composition of this invention to
provide bit lubrication, heat removal and cutting removal and to
increase an aggregation potential or zeta potential of any
particulate solid including metal oxide-containing solid in the
drilling fluid or that becomes entrained in the drilling fluid to
increase solids removal. After passing through the structure that
produces an undesired quantities of particulate metal
oxide-containing solids, change the second drilling fluid for the
first drilling fluid or a third drilling fluid.
Method for Producing
[0042] The present invention also broadly relates to a method for
producing including the step of circulating and/or pumping a fluid
into, where the fluid includes a composition of this invention,
which increases an aggregation potential or decreases an absolute
value of the zeta potential of any particulate solid including a
metal oxide-containing solid in the fluid or that becomes entrained
in the fluid to increase solids removal and to decrease the
potential of the particles plugging the formation and/or production
tubing.
Suitable Agents
[0043] Suitable amines include, without limitation, any amine that
is capable of reacting with a suitable phosphate containing
compound to form a composition that forms a deformable coating on a
metal-oxide-containing surface. Exemplary examples of such amines
include, without limitation, any amine of the general formula
R.sup.1,R.sup.2NH or mixtures or combinations thereof, where
R.sup.1 and R.sup.2 are independently a hydrogen atom or a carbyl
group having between about between about 1 and 40 carbon atoms and
the required hydrogen atoms to satisfy the valence and where one or
more of the carbon atoms can be replaced by one or more hetero
atoms selected from the group consisting of boron, nitrogen,
oxygen, phosphorus, sulfur or mixture or combinations thereof and
where one or more of the hydrogen atoms can be replaced by one or
more single valence atoms selected from the group consisting of
fluorine, chlorine, bromine, iodine or mixtures or combinations
thereof. Exemplary examples of amines suitable for use in this
invention include, without limitation, aniline and alkyl anilines
or mixtures of alkyl anilines, pyridines and alkyl pyridines or
mixtures of alkyl pyridines, pyrrole and alkyl pyrroles or mixtures
of alkyl pyrroles, piperidine and alkyl piperidines or mixtures of
alkyl piperidines, pyrrolidine and alkyl pyrrolidines or mixtures
of alkyl pyrrolidines, indole and alkyl indoles or mixture of alkyl
indoles, imidazole and alkyl imidazole or mixtures of alkyl
imidazole, quinoline and alkyl quinoline or mixture of alkyl
quinoline, isoquinoline and alkyl isoquinoline or mixture of alkyl
isoquinoline, pyrazine and alkyl pyrazine or mixture of alkyl
pyrazine, quinoxaline and alkyl quinoxaline or mixture of alkyl
quinoxaline, acridine and alkyl acridine or mixture of alkyl
acridine, pyrimidine and alkyl pyrimidine or mixture of alkyl
pyrimidine, quinazoline and alkyl quinazoline or mixture of alkyl
quinazoline, or mixtures or combinations thereof.
[0044] Suitable phosphate containing compounds include, without
limitation, any phosphate acid and/or any phosphate ester that is
capable of reacting with a suitable amine to form a composition
that forms a deformable coating on a metal-oxide containing surface
or partially or completely coats particulate materials. Exemplary
examples of such phosphate esters include, without limitation, any
phosphate esters of the general formula
P(O)(OR.sup.3)(OR.sup.4)(OR.sup.5) or mixture or combinations
thereof, where R.sup.3, R.sup.4, and OR.sup.5 are independently a
hydrogen atom or a carbyl group having between about between about
1 and 40 carbon atoms and the required hydrogen atoms to satisfy
the valence and where one or more of the carbon atoms can be
replaced by one or more hetero atoms selected from the group
consisting of boron, nitrogen, oxygen, phosphorus, sulfur or
mixture or combinations thereof and where one or more of the
hydrogen atoms can be replaced by one or more single valence atoms
selected from the group consisting of fluorine, chlorine, bromine,
iodine or mixtures or combinations thereof. Exemplary examples of
phosphate esters include, without limitation, phosphate ester of
alkanols having the general formula P(O)(OH).sub.x(OR.sup.6).sub.y
where x+y=3 and are independently a hydrogen atom or a carbyl group
having between about between about 1 and 40 carbon atoms and the
required hydrogen atoms to satisfy the valence and where one or
more of the carbon atoms can be replaced by one or more hetero
atoms selected from the group consisting of boron, nitrogen,
oxygen, phosphorus, sulfur or mixture or combinations thereof and
where one or more of the hydrogen atoms can be replaced by one or
more single valence atoms selected from the group consisting of
fluorine, chlorine, bromine, iodine or mixtures or combinations
thereof such as ethoxy phosphate, propoxyl phosphate or higher
alkoxy phosphates or mixtures or combinations thereof. Other
exemplary examples of phosphate esters include, without limitation,
phosphate esters of alkanol amines having the general formula
N[R.sup.7OP(O)(OH).sub.2].sub.3 where R.sup.7 is a carbenzyl group
having between about between about 1 and 40 carbon atoms and the
required hydrogen atoms to satisfy the valence and where one or
more of the carbon atoms can be replaced by one or more hetero
atoms selected from the group consisting of boron, nitrogen,
oxygen, phosphorus, sulfur or mixture or combinations thereof and
where one or more of the hydrogen atoms can be replaced by one or
more single valence atoms selected from the group consisting of
fluorine, chlorine, bromine, iodine or mixtures or combinations
thereof group including the tri-phosphate ester of tri-ethanol
amine or mixtures or combinations thereof. Other exemplary examples
of phosphate esters include, without limitation, phosphate esters
of hydroxylated aromatics such as phosphate esters of alkylated
phenols such as Nonylphenyl phosphate ester or phenolic phosphate
esters. Other exemplary examples of phosphate esters include,
without limitation, phosphate esters of diols and polyols such as
phosphate esters of ethylene glycol, propylene glycol, or higher
glycolic structures. Other exemplary phosphate esters include any
phosphate ester than can react with an amine and coated on to a
substrate forms a deformable coating enhancing the aggregating
potential of the substrate. Exemplary phosphate acids include
phosphoric acid, polyphosphoric acid or mixtures thereof.
[0045] Suitable solid materials suitable for being coated with the
compositions of this invention include, without limitation, metal
oxides and/or ceramics, natural or synthetic, metals, plastics
and/or other polymeric solids, solid materials derived from plants,
or any other solid material that does or may find use in downhole
applications or mixtures or combinations thereof. Metal oxides
including any solid oxide of a metallic element of the periodic
table of elements. Exemplary examples of metal oxides and ceramics
include actinium oxides, aluminum oxides, antimony oxides, boron
oxides, barium oxides, bismuth oxides, calcium oxides, cerium
oxides, cobalt oxides, chromium oxides, cesium oxides, copper
oxides, dysprosium oxides, erbium oxides, europium oxides, gallium
oxides, germanium oxides, iridium oxides, iron oxides, lanthanum
oxides, lithium oxides, magnesium oxides, manganese oxides,
molybdenum oxides, niobium oxides, neodymium oxides, nickel oxides,
osmium oxides, palladium oxides, potassium oxides, promethium
oxides, praseodymium oxides, platinum oxides, rubidium oxides,
rhenium oxides, rhodium oxides, ruthenium oxides, scandium oxides,
selenium oxides, silicon oxides, samarium oxides, silver oxides,
sodium oxides, strontium oxides, tantalum oxides, terbium oxides,
tellurium oxides, thorium oxides, tin oxides, titanium oxides,
thallium oxides, thulium oxides, vanadium oxides, tungsten oxides,
yttrium oxides, ytterbium oxides, zinc oxides, zirconium oxides,
ceramic structures prepared from one or more of these oxides and
mixed metal oxides including two or more of the above listed metal
oxides. Exemplary examples of plant materials include, without
limitation, shells of seed bearing plants such as walnut shells,
pecan shells, peanut shells, shells for other hard shelled seed
forming plants, ground wood or other fibrous cellulosic materials,
or mixtures or combinations thereof.
[0046] Suitable polymers for use in the compositions of this
invention includes, without limitation, any polymer including
repeat units derived from a heterocyclic or heterocyclic aromatic
vinyl monomer, where the hetero atoms is a nitrogen atom or a
combination of a nitrogen atom and another hetero atoms selected
from the group consisting of boron, oxygen, phosphorus, sulfur,
germanium, and/or. The polymers can be homopolymers of cyclic or
aromatic nitrogen-containing vinyl monomers, or copolymers of any
ethylenically unsaturated monomers that will copolymerize with a
cyclic or aromatic nitrogen-containing vinyl monomer. Exemplary
cyclic or aromatic nitrogen-containing vinyl monomers include,
without limitation, vinyl pyrroles, substituted vinyl pyrroles,
vinyl pyridines, substituted vinyl pyridines, vinyl quinolines or
substituted vinyl quinolines, vinyl anilines or substituted vinyl
anilines, vinyl piperidines or substituted vinyl piperidines, vinyl
pirrolidines or substituted vinyl pyrrolidines, vinyl imidazole or
substituted vinyl imidazole, vinyl pyrazine or substituted vinyl
pyrazines, vinyl pyrimidine or substituted vinyl pyrimidine, vinyl
quinazoline or substituted vinyl quinazoline, or mixtures or
combinations thereof. Exemplary pyridine monomer include 2-vinyl
pyridine, 4-vinyl pyridine, or mixtures or combinations thereof.
Exemplary homopolymers include poly-2-vinyl pyridine, poly-4-vinyl
pyridine, and mixtures or combinations thereof. Exemplary
copolymers including copolymers or 2-vinyl pyridine and 4-vinyl
pyridine, copolymers of ethylene and 2-vinyl pyridine and/or
4-vinyl pyridine, copolymers of propylene and 2-vinyl pyridine
and/or 4-vinyl pyridine, copolymers of acrylic acid and 2-vinyl
pyridine and/or 4-vinyl pyridine, copolymers of methacrylic acid
and 2-vinyl pyridine and/or 4-vinyl pyridine, copolymers of
acrylates and 2-vinyl pyridine and/or 4-vinyl pyridine, copolymers
of methacrylates and 2-vinyl pyridine and/or 4-vinyl pyridine, and
mixtures of combinations thereof. All of these monomers can also
includes substituents. Moreover, in all these vinyl monomers or
ethylenically unsaturated monomers, one or more of the carbon atoms
can be replaced by one or more hetero atoms selected from the group
consisting of boron, oxygen, phosphorus, sulfur or mixture or
combinations thereof and where one or more of the hydrogen atoms
can be replaced by one or more single valence atoms selected from
the group consisting of fluorine, chlorine, bromine, iodine or
mixtures or combinations thereof. Of course, all of these monomers
includes at least one nitrogen atom in the structure.
EXPERIMENTS OF THE INVENTION
Purpose
[0047] We have evaluated sand aggregation and gas regain
permeability in core flooding tests of formulation 1 due changes in
the Zeta Potential.
Formulation 1
Ingredients and Weight Percentages for Formulation 1
TABLE-US-00001 [0048] Components wt. % PAP-220.sup..dagger. 44.72
Phosphate Ester.sup..dagger-dbl. 4.87 Methanol 40.41 Reilline 410*
10.00 .sup..dagger.Mixture of alkyl pyridines available from
Vertellus .sup..dagger-dbl.Reaction product of 78.50 wt. %
polyphosphoric acid and 21.50 wt. % tri-ethanol amine *Mixture of
poly 4 vinyl pyridine available from Vertellus
Procedure
Agglomeration Properties
[0049] Treated and un-treated sand were tested by mixing 250 grams
of 20/40 Badger sand in slurries with concentrations of 6 gal of
Formulation 1 per 1000 lb of sand.
[0050] The sand was rinsed three times and poured into a clear PVC
plastic cylinder.
Core Flooding Tests
[0051] Core tests were conducted in Berea Sand Stone cores of
permeability to N.sub.2 of 50-55 mD. The core same was 1.5 inches
diameter and 3.5 inches long.
[0052] The tests were started by measuring permeability to brine at
a flow rate of 120 cc/min until 5 porous volume were collected and
checking the Darcy Flow regime.
[0053] Flow of nitrogen was started with a differential pressure of
10 psi recording liquid collected in the other end of the core as
well as gas flow rate for two hours.
[0054] Liquid saturation was then reestablished, when injecting 5
porous volume of the treated brine with the load recovering
agent.
[0055] Flow of nitrogen was then re-started with a differential
pressure of 10 psi measuring collected liquid and gas flow rate in
the other end of the core.
[0056] In all the tests, the overburden pressure was set in the
radial and axial direction of 1000 psi and the temperature at
70.degree. F.
Results
[0057] Referring FIG. 1 compares the agglomeration properties of
20/40 sand before treated and after treated with formulation 1
using 6 gal of treating system per 1000 lb of. In this case, it can
be clearly observed that treated sand did not fall when turned the
plastic cylinder down.
[0058] Referring to FIG. 2, a diagram of Core Test Apparatus for
determining liquid permeability is shown, while FIG. 3, a diagram
of Core Test Apparatus for determining gas permeability.
[0059] Referring FIG. 4 compares the agglomeration properties of
20/40 sand before treated and after treated with formulation 1
using 6 gal of treating system per 1000 lb of. In this case it can
be clearly observed that treated sand did not fall when turned the
plastic cylinder down.
[0060] All references cited herein are incorporated by reference.
Although the invention has been disclosed with reference to its
preferred embodiments, from reading this description those of skill
in the art may appreciate changes and modification that may be made
which do not depart from the scope and spirit of the invention as
described above and claimed hereafter.
* * * * *