U.S. patent application number 15/876823 was filed with the patent office on 2018-07-26 for method to consolidate solid materials during subterranean treatment operations.
The applicant listed for this patent is The Lubrizol Corporation. Invention is credited to Chih-Chau Hwang, Rajesh K. Saini, Mathew M. Samuel, Clayton S. Smith, Kern L. Smith, Duane Treybig, Leonid Vigderman.
Application Number | 20180209260 15/876823 |
Document ID | / |
Family ID | 52624386 |
Filed Date | 2018-07-26 |
United States Patent
Application |
20180209260 |
Kind Code |
A1 |
Hwang; Chih-Chau ; et
al. |
July 26, 2018 |
Method to Consolidate Solid Materials During Subterranean Treatment
Operations
Abstract
Compositions include (1) aggregating compositions capable of
forming deformable partial or complete coatings on formation
surfaces, formation particle surfaces, downhole fluid solid
surfaces, and/or proppant surfaces, where the coatings increase
aggregation and/or agglomeration propensities of the particles and
surfaces to form particles clusters or pillars having deformable
coatings, and (2) aggregation stabilizing and/or strengthening
compositions capable of altering properties of the coated clusters
or pillars to form consolidated, stabilized, and/or strengthened
clusters or pillars. Methods for stabilizing aggregated particle
clusters or pillars include (1) treating the particles with an
aggregating composition to form aggregated clusters or pillars and
(2) treating the aggregated particle clusters or pillars with a
stabilizing or strengthening composition to form consolidated,
stabilized, and/or strengthened clusters or pillars.
Inventors: |
Hwang; Chih-Chau; (Houston,
TX) ; Saini; Rajesh K.; (Cypress, TX) ;
Vigderman; Leonid; (Baytown, TX) ; Treybig;
Duane; (Spring, TX) ; Smith; Clayton S.;
(Houston, TX) ; Samuel; Mathew M.; (Sugar Land,
TX) ; Smith; Kern L.; (The Woodlands, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Lubrizol Corporation |
Wickliffe |
OH |
US |
|
|
Family ID: |
52624386 |
Appl. No.: |
15/876823 |
Filed: |
January 22, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14546288 |
Nov 18, 2014 |
9909404 |
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15876823 |
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14308160 |
Jun 18, 2014 |
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14546288 |
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13914513 |
Jun 10, 2013 |
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14546288 |
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13914526 |
Jun 10, 2013 |
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13914513 |
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12690292 |
Jan 20, 2010 |
8950493 |
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13914526 |
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12247985 |
Oct 8, 2008 |
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12690292 |
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61905340 |
Nov 18, 2013 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K 8/92 20130101; C09K
2208/08 20130101; C09K 8/685 20130101; C09K 8/805 20130101; E21B
43/267 20130101; C09K 8/887 20130101; C09K 2208/18 20130101; C09K
8/70 20130101; C09K 8/80 20130101 |
International
Class: |
E21B 43/267 20060101
E21B043/267; C09K 8/88 20060101 C09K008/88; C09K 8/70 20060101
C09K008/70; C09K 8/92 20060101 C09K008/92; C09K 8/68 20060101
C09K008/68; C09K 8/80 20060101 C09K008/80 |
Claims
1. A composition comprising: (1) zeta potential altering or
aggregating composition consisting of 1) an amine/phosphate
reaction product, 2) at amine component and an amine/phosphate
reaction product, 3) a polymeric amine; 4) a polymeric amine and an
amine/phosphate reaction product, 5) a polymeric amine, an amine
component, and an amine/phosphate reaction product, 6) an amine
component, and a coating crosslinking composition comprising an
inorganic crosslinking agent, an organic crosslinking agent, or
mixtures and combinations thereof, wherein the amine component is
selected from the group consisting of alkyl pyridines or mixtures
of alkyl pyridines, alkyl pyrroles or mixtures of alkyl pyrroles,
alkyl piperidines or mixtures of alkyl piperidines, alkyl
pyrrolidines or mixtures of alkyl pyrrolidines, alkyl indolizines
or mixture of alkyl indolizines, alkyl indoles or mixture of alkyl
indoles, alkyl imidazole or mixtures of alkyl imidazole, alkyl
quinoline or mixture of alkyl quinoline, alkyl isoquinoline or
mixture of alkyl isoquinoline, alkyl pyrazine or mixture of alkyl
pyrazine, alkyl quinoxaline or mixture of alkyl quinoxaline, alkyl
acridine or mixture of alkyl acridine, alkyl pyrimidine or mixture
of alkyl pyrimidine, alkyl quinazoline or mixture of alkyl
quinazoline, or mixtures and combinations thereof.
2-41. (canceled)
Description
RELATED APPLICATIONS
[0001] The present invention claim provisional priority to and the
benefit of U.S. Provisional Patent Application Ser. No. 61/905,340
filed 18 Nov. 2013 and continuations-in-part of U.S. patent
application Ser. No. 12/690,292 filed Jan. 20, 2010, Ser. No.
13/914,513 filed Jun. 10, 2013, Ser. No. 13/914,526 filed Jun. 10,
2013, Ser. No. 14/308,160 filed Jun. 18, 2014, and Ser. No.
12/247,985 filed Sep. 28, 2011.
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0002] Embodiments of this invention relate to compositions of
crosslinked zeta potential altering coated proppant and methods for
sand packing, frac packing, fracturing, formation consolidation,
and producing fluids from subterranean formation using crosslinked
zeta potential altering coated proppant and methods for producing
from a formation through the formation of a network of proppant
pillars, clusters, columns, or islands in fractures in a formation
during and/or after formation fracturing, proppant networks,
proppant pillars, coating crosslinking composition, crosslinked
coatings, and crosslinked coated proppants.
[0003] More particularly, embodiments of this invention relate to
compositions of crosslinked zeta potential altering coated proppant
and methods for sand packing, frac packing, fracturing, formation
consolidation, and producing fluids from subterranean formation
using crosslinked zeta potential altering coated proppant and
methods for producing fluids from subterranean formations through
the formation of a network of proppant pillars, clusters, columns,
or islands in fractures in a formation during and/or after
formation fracturing, proppant networks, proppant pillars, coating
crosslinking composition, crosslinked coatings, and crosslinked
coated proppants, where the methods include a sequence of proppant
stages designed to form proppant networks and proppant pillars that
increase fracture conductivity. The embodiment of this invention
also relate to proppant and fines control where the formation or
proppant pack is treated with zeta altering material of the present
invention and then consolidation with the crosslinking agent to
provide strength to proppant pack or formation and also prevent
fines migration by modifying zeta potential of the fines particles
so as to produce fluid at a much greater draw down rate.
2. Description of the Related Art
[0004] Many techniques related to sand control have been proposed
to decrease proppant flow back in order to sustain high
conductivity fractures after hydraulic fracturing. One technique
includes Halliburton deposited thermally-cured proppants in the
fracture, and resin-coated gravel, for example, to create a
fracture with high conductivity. These resin coated proppants are
designed to prevent proppant flowback and to reduce fines
generation and migration when cured at high temperature and
pressure. A second technique includes coating the proppant with
liquid resin containing crosslinking agent and pumping the coated
proppant downhole during fracturing and allowing the thermoset
resin to harden with temperature to create bound proppant pack. In
situ consolidation of proppant with liquid thermoset resin
injection that cement the proppants in situ provide poor
conductivity and is not used too often. Most commercially available
systems employ phenolic, furan, or epoxy resins mixed with the
crosslinking agent that is activated by formation temperature.
These techniques bind rock particles together, creating a stable
matrix of permeable, consolidated grains. A third technique
includes prepacked screens and slotted liners, especially for
friable or completely unconsolidated formations, prepacked screens
and slotted liners provide a low-cost downhole filtering and many
other techniques used to prevent proppants from flowback, thereby
enhancing the productivity during fracturing applications.
[0005] While there are a number of solutions to the problem of
proppant flowback, these solutions either require special proppants
or required resin cementing of proppant in the formation. These
techniques have different drawbacks such as enhanced proppant
expense and rigid refashioning of formation properties due to
internal cementing. They also reduce the porosity and conductivity
of the proppant pack or unconsolidated formation. Also it is
difficult to use these techniques in remedial treatment of proppant
pack of formation due to accumulation of these resins in the pores.
Thus, there is a need in the art for a different technique for
dealing with proppant flowback. Moreover, thermoset resin system
described previously cannot be used in the control of fines
migration as resin can set in the pores and will plug the
formation. They also do not capture the fines because they set into
a hard coating with no affinity for fines material.
SUMMARY OF THE INVENTION
[0006] Embodiments of this invention provide compositions
including: (1) aggregating compositions capable of forming
deformable partial or complete coatings on formation surfaces,
formation particle surfaces, downhole fluid solid surfaces, and/or
proppant surfaces, where the coatings increase aggregation and/or
agglomeration propensities of the particles and surfaces to form
particles clusters or pillars having deformable coatings, and (2)
aggregation stabilizing and/or strengthening compositions capable
of altering properties of the coated clusters or pillars to form
consolidated, stabilized, and/or strengthened clusters or pillars.
The stabilized and/or strengthening proppant materials may be used
in fracturing applications, frac pack applications, slick water
applications, sand pack applications, formation consolidation
application for consolidating unconsolidated or weakly consolidated
formations, or any other application where proppant having a
strengthened zeta potential altering coating (partial or complete)
would be applicable. In all of these applications, the aggregating
compositions and coating crosslinking compositions may be added to
the treating fluids at any time during the treatments and alone or
in combination. Generally, the coating crosslinking compositions
will be used after the zeta potential altering compositions or
after the injection of proppant treated with the zeta potential
altering compositions. In some cases crosslinking compositions can
be intimately mixed with the zeta particle altering composition so
as to treat as one component system. This composition is tailored
to give a delayed consolidation or crosslinking effect either
triggered by heat or time.
[0007] Embodiments of this invention provide methods for
stabilizing aggregated particle clusters or pillars by (1) treating
the particles with an aggregating composition to form aggregated
clusters or pillars and (2) treating the aggregated particle
clusters or pillars with a stabilizing or strengthening composition
to form consolidated, stabilized, and/or strengthened clusters or
pillars.
[0008] Embodiments of this invention provide methods for forming
proppant pillars in a formation during formation fracturing, where
the methods include a sequence of injections of one fracturing
fluid or a plurality of different fracturing fluids, where the
fracturing fluids are selected from the group consisting of fluids
that include a proppant and a zeta altering or aggregating
composition, fluids that do not include the proppant and the zeta
altering or aggregating composition, fluids that include the zeta
altering or aggregating composition, but no proppant, and fluids
that include a proppant, but no zeta altering or aggregating
composition. The sequences may include single injections of each
fluid in any order or multiple injections of each fluid in any
order. Thus, one sequence may include injecting a first fluid
including no proppant, injection a second fluid including the zeta
altering or aggregating composition, but no proppant, and a third
fluid including the proppant and the zeta altering or aggregating
composition. The fluids including a proppant may include untreated
proppant, treated proppant comprising particles coated or partially
coated with the zeta altering or aggregating composition, or
mixtures thereof. Another sequence may include a plurality of first
fluid injections, a plurality of second fluid injections, and a
plurality of third fluid injections. Another sequence may include
single injections of the first, second, and third fluids repeated a
number of times during the course of the proppant placement stage
of a fracturing operation. Another sequence may include multiple
injections of each fluid in any given order. The sequence may also
include a hold period between each injection. Thus, a sequence may
include a first fluid injection, a first hold time, a second fluid
injection, a second hold time, and a third fluid injection, and a
third hold time, where the first, second and third fluid may be any
of the fluid compositions listed above.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] 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:
[0010] FIG. 1A depicts an embodiment of a fracturing profile of
this invention.
[0011] FIG. 1B depicts another embodiment of a fracturing profile
of this invention.
[0012] FIG. 1C depicts another embodiment of a fracturing profile
of this invention.
[0013] FIG. 1D depicts another embodiment of a fracturing profile
of this invention.
[0014] FIG. 2A depicts an embodiment a proppant pattern or network
within a board fracture.
[0015] FIG. 2B depicts an embodiment a proppant pattern or network
within a narrow fracture.
[0016] FIG. 2C depicts an embodiment a proppant pattern or network
within an illustrative square fracture.
[0017] FIG. 2D depicts an embodiment a proppant pattern or network
within a branched fracture.
[0018] FIG. 2E depicts an embodiment a proppant pattern or network
within a frac pack.
[0019] FIGS. 3A-I depict nine different illustrative proppant
clusters.
[0020] FIGS. 4A-J depict ten different proppant groups of proppant
clusters.
[0021] FIGS. 5A-D depict four different perforation patterns.
[0022] FIG. 6 depicts a table of zeta potentials and aggregating
propensities and a plot of zeta potentials for untreated silica and
coal and treated silica and coal.
[0023] FIG. 7A depicts a photograph of untreated 200 mesh silica
sand.
[0024] FIG. 7B depicts a photograph of 200 mesh silica sand treated
with a 7 wt. % SandAid.TM. solution.
[0025] FIG. 7C depicts a photograph of 200 mesh silica sand treated
with a 7 wt. % SandAid.TM. solution and a SandAid.TM. crosslinking
composition.
[0026] FIG. 8A depicts a photograph of 200 mesh sand treated with
SandAid.TM. topped with water in a 4 oz bottle.
[0027] FIG. 8B depicts a photograph of 200 mesh sand treated with
SandAid.TM. and a SandAid.TM. crosslinking composition topped with
water in a 4 oz bottle.
[0028] FIG. 8C depicts a photograph of bottle of FIG. 8A inverted
showing a portion of the aggregated sand had fallen to the capped
end of the bottle.
[0029] FIG. 8D depicts a photograph of bottle of FIG. 8B inverted
showing that none of the sand fell to the capped end of the
bottle.
[0030] FIG. 9A depicts photographs of SandAid treated
CARBOLITE.RTM. ceramic proppant topped with water in a 4 oz bottle
upright.
[0031] FIG. 9B depicts photographs of bottle of FIG. 9A after high
temperature (137.degree. C.) and pressure treatment (420 psi) in a
4 oz bottle upright.
[0032] FIG. 9C depicts photographs of crosslinked SandAid.TM.
treated CARBOLITE.RTM. ceramic proppant topped with water in a 4 oz
bottle inverted.
[0033] FIG. 9D depicts photographs of bottle of FIG. 9C after high
temperature (137.degree. C.) and pressure treatment (420 psi) in a
4 oz bottle inverted.
[0034] FIG. 10 depicts a photograph of SandAid.TM. treated 200 mesh
sand (upper cylindrical block) and crosslinked SandAid.TM. treated
200 mesh sand (lower cylindrical block) stacked on top of each
other after MSFR testing (MSFRT).
[0035] FIG. 11A depicts a photograph of a SandAid.TM. treated sand
core after regain permeability testing.
[0036] FIG. 11B depicts a photograph of a crosslinked SandAid.TM.
treated sand core after regain permeability testing.
DEFINITIONS OF TERM USED IN THE INVENTION
[0037] The following definitions are provided in order to aid those
skilled in the art in understanding the detailed description of the
present invention.
[0038] The term "about" means that the value is within about 10% of
the indicated value. In certain embodiments, the value is within
about 5% of the indicated value. In certain embodiments, the value
is within about 2.5% of the indicated value. In certain
embodiments, the value is within about 1% of the indicated value.
In certain embodiments, the value is within about 0.5% of the
indicated value.
[0039] The term "substantially" means that the value is within
about 10% of the indicated value. In certain embodiments, the value
is within about 5% of the indicated value. In certain embodiments,
the value is within about 2.5% of the indicated value. In certain
embodiments, the value is within about 1% of the indicated value.
In certain embodiments, the value is within about 0.5% of the
indicated value.
[0040] The term "proppant pillar, proppant island, proppant
cluster, proppant aggregate, or proppant agglomerate" mean that a
plurality of proppant particles are aggregated, clustered,
agglomerated or otherwise adhered together to form discrete
structures.
[0041] The term "mobile or re-healing proppant pillar, proppant
island, proppant cluster, proppant aggregate, or proppant
agglomerate" means proppant pillar, proppant island, proppant
cluster, proppant aggregate, or proppant agglomerate that are
capable of repositioning during fracturing, producing, or injecting
operations.
[0042] The term "self healing proppant pillar, proppant island,
proppant cluster, proppant aggregate, or proppant agglomerate"
means proppant pillar, proppant island, proppant cluster, proppant
aggregate, or proppant agglomerate that are capable of being broken
apart and recombining during fracturing, producing, or injecting
operations.
[0043] The term "amphoteric" refers to surfactants that have both
positive and negative charges. The net charge of the surfactant can
be positive, negative, or neutral, depending on the pH of the
solution.
[0044] The term "anionic" refers to those viscoelastic surfactants
that possess a net negative charge.
[0045] The term "fracturing" refers to the process and methods of
breaking down a geological formation, i.e. the rock formation
around a well bore, by pumping fluid at very high pressures, in
order to increase production rates from a hydrocarbon reservoir.
The fracturing methods of this invention use otherwise conventional
techniques known in the art.
[0046] The term "proppant" refers to a granular substance suspended
in the fracturing fluid during the fracturing operation, which
serves to keep the formation from closing back down upon itself
once the pressure is released. Proppants envisioned by the present
invention include, but are not limited to, conventional proppants
familiar to those skilled in the art such as sand, 20-40 mesh sand,
resin-coated sand, sintered bauxite, glass beads, and similar
materials.
[0047] The abbreviation "RPM" refers to relative permeability
modifiers.
[0048] The term "surfactant" refers to a soluble, or partially
soluble compound that reduces the surface tension of liquids, or
reduces inter-facial tension between two liquids, or a liquid and a
solid by congregating and orienting itself at these interfaces.
[0049] The term "viscoelastic" refers to those viscous fluids
having elastic properties, i.e., the liquid at least partially
returns to its original form when an applied stress is
released.
[0050] The phrase "viscoelastic surfactants" or "VES" refers to
that class of compounds which can form micelles (spherulitic,
anisometric, lamellar, or liquid crystal) in the presence of
counter ions in aqueous solutions, thereby imparting viscosity to
the fluid. Anisometric micelles in particular are preferred, as
their behavior in solution most closely resembles that of a
polymer.
[0051] The abbreviation "VAS" refers to a Viscoelastic Anionic
Surfactant, useful for fracturing operations and frac packing. As
discussed herein, they have an anionic nature with preferred
counterions of potassium, ammonium, sodium, calcium or
magnesium.
[0052] The term "foamable" means a composition that when mixed with
a gas forms a stable foam.
[0053] The term "fracturing layer" is used to designate a layer, or
layers, of rock that are intended to be fractured in a single
fracturing treatment. It is important to understand that a
"fracturing layer" may include one or more than one of rock layers
or strata as typically defined by differences in permeability, rock
type, porosity, grain size, Young's modulus, fluid content, or any
of many other parameters. That is, a "fracturing layer" is the rock
layer or layers in contact with all the perforations through which
fluid is forced into the rock in a given treatment. The operator
may choose to fracture, at one time, a "fracturing layer" that
includes water zones and hydrocarbon zones, and/or high
permeability and low permeability zones (or even impermeable zones
such as shale zones) etc. Thus a "fracturing layer" may contain
multiple regions that are conventionally called individual layers,
strata, zones, streaks, pay zones, etc., and we use such terms in
their conventional manner to describe parts of a fracturing layer.
Typically the fracturing layer contains a hydrocarbon reservoir,
but the methods may also be used for fracturing water wells,
storage wells, injection wells, etc. Note also that some
embodiments of the invention are described in terms of conventional
circular perforations (for example, as created with shaped
charges), normally having perforation tunnels. However, the
invention is may also be practiced with other types of
"perforations", for example openings or slots cut into the tubing
by jetting.
[0054] The term MSFR means maximum sand free production rate, which
is the maximum production rate that can be achieved in a well
without the co-production of sand or formation particulate.
[0055] The term cavitation or cavitating means to form cavities
around production tubing, casing or cemented casing, i.e., to
produce a volume free of sand surrounding the production tubing,
casing or cemented casing.
[0056] The term cavitated formation is a formation having a cavity
or cavities surrounding the production tubing, casing or cemented
casing.
[0057] The term draw down pressure means a reduction in a pressure
that is required to move the content, such as but not limited to,
oil, gas and/or water, of the formation or zone into the casing,
liner or tubing.
[0058] The term critical draw down pressure means the reduction in
a pressure that is required to produce formation particulate, such
as but not limited to, silica, clay, sand, and/or fines, into the
casing or liner or tubing.
[0059] The term aggregated, agglomerated or conglomerated formation
means that the weakly consolidated, semi-consolidated or
unconsolidated formation has been treated with an aggregation,
agglomeration, or conglomeration composition so that the formation
is stable enough to produce below its critical draw down pressure
without collapse.
[0060] The term relative draw down pressure means draw down
pressure per unit area of the producible formation or zone.
[0061] The term "gpt" means gallons per thousand gallons.
[0062] The term "ppt" means pounds per thousand gallons.
DETAILED DESCRIPTION OF THE INVENTION
[0063] The inventors have found that a new and different solution
to sand control or proppant flowback not based on either
thermosetting plastic proppants or in situ resin injection. The new
approach involves metal stabilization of aggregating compositions
that form partial or complete coatings on formation surfaces,
formation particulates, proppants, or mixtures thereof to increase
their aggregation propensity. The aggregating compositions include
1) amine/phosphate reaction products, 2) an amine component and
amine/phosphate reaction products, 3) polymeric amines; 4)
polymeric amines and amine/phosphate reaction products, 5)
polymeric amines, an amine component, and amine/phosphate reaction
products, 6) amine component, or 7) mixtures and combinations
thereof. The inventors believe that the transition metals become
complexed into the aggregating composition coating to form metal
stabilized, consolidated, and/or strengthened aggregating
composition coatings. Thus, once the metal salts are applied to the
aggregating composition coating or coated proppants, a texture
and/or chemical/physical properties and characteristics of
treatedproppants change. The texture and/or chemical/physical
properties become consolidated, stabilized, and/or strengthened due
to formation of a network structure of metal complexes in the
aggregating composition coatings. The inventors have found that the
addition of metal salts to the aggregating composition coatings
improve both thermal and/or mechanical properties and
characteristics of the aggregating composition coatings used in
this invention. For further details on the aggregating compositions
used in this invention the reader is referred to U.S. Pat. Nos.
7,392,847; 7,956,017; 8,466,094; and 8,871,694; and United States
Pub. Nos. 20100212905, and 20130075100.
[0064] Embodiments of this invention relates to compositions
including: (1) zeta potential altering or aggregating composition
capable of forming deformable partial or complete coatings on
formation surfaces, formation particle surfaces, downhole fluid
solid surfaces, and/or proppant surfaces, where the coatings
increase aggregation and/or agglomeration propensities of the
particles and surfaces to form particles clusters or pillars having
deformable coatings, and (2) aggregation stabilizing and/or
strengthening compositions capable of altering properties of the
coated clusters or pillars to form consolidated, stabilized, and/or
strengthened clusters or pillars, where the stabilized and/or
strengthening proppant materials may be used in fracturing
applications, frac pack applications, slick water applications,
sand pack applications, formation consolidation application for
consolidating unconsolidated or weakly consolidated formations, or
any other application where proppant having a strengthened zeta
potential altering coating (partial or complete) would be
applicable, where the aggregating composition and coating
crosslinking composition may be added to the treating fluids at any
time during the treatments and alone or in combination, provided
that the coating crosslinking compositions is used after the zeta
potential altering compositions or after the injection of proppant
treated with the zeta potential altering compositions.
[0065] Hydraulic fractures are formed by pumping a fracturing fluid
into a wellbore at a rate sufficient to increase a target zone
downhole pressure to the point of causing or inducing fractures
into the target zone of the formation. Small grains of fracturing
proppants, injected with or during fracturing, act to hold open the
pressure formed fractures, preventing the fractures from closing,
when the injection is stopped and the hydraulic pressure of the
fluid is removed. However, poorly consolidated proppants can be
easily produced overtime thus reducing the fracture width and thus
losing the conductivity. The production of sand or fines can lead
to erosion of perforations and also tubulars and pumps which leads
to costly repairs. The goal of this invention is to enhance the
efficacy of sand control by consolidating fracturing proppants to
preclude the possibility ofproppant flow back and maximize the
fracture flow capacity.
[0066] This invention describes the achievement of high
conductivity fracture using crosslinking chemistry to consolidate
the structure of amine-phosphate aggregating coating on fracturing
proppants. Typically, fracturing fluids with amine-phosphate
aggregating composition treated proppants will be pumped into a
well to form agglomerated proppant clusters during a fracturing
operation. Through post flushing the agglomerated clusters with
transition metal salt solutions, the texture of the proppant
clusters can be drastically altered increasing their extent of
consolidation to form consolidated proppant clusters comprised of
metal stabilized aggregates of amine-phosphate reaction product
coated proppants. Amine-phosphate reaction product treated
proppants are soft-touching clusters, meaning that the coatings are
deformable and soft to the touch. After treating with a transition
metal salt solution, the coatings are transformed into a hard and
lumpy proppant clusters, which eliminate the possibility of
proppant flowback as well as improve fracturing conductivity during
subsequent production.
[0067] The statements in this section merely provide background
information related to the present disclosure and may not
constitute prior art.
[0068] The invention relates to production of fluids from
subterranean formations. More particularly, it relates to
stimulation of flow through formations by hydraulic fracturing.
Most particularly, it relates to methods of optimizing fracture
conductivity by propping fractures in a formation stratum so that
the proppant is distributed heterogeneously in the fracture, and in
some embodiments, the fracture containing substantial voids with
little or no proppant.
[0069] Embodiments of methods of this invention provide a proppant
placement step involving injecting alternating slugs of
proppant-free fluids and proppant-containing fluids into fractures
of the fracturing layer above fracturing pressure through a number
of perforation groups. The slugs of proppant-containing fluids form
proppant pillars, clusters, or islands in the fractures during
fracturing and/or after fracturing as the fractures closes.
[0070] Embodiments of methods of this invention provide a proppant
placement step involving injecting alternating slugs of
proppant-free fluids and proppant-containing fluids into the
fractures of the fracturing layer above fracturing pressure through
a number of perforation groups in a wellbore, and causing the
sequences of slugs of proppant-free fluids and proppant-containing
fluids injected through neighboring perforation groups to move
through the fractures at different rates. The slugs of
proppant-containing fluids again form proppant pillars, clusters,
or island in the fractures during fracturing and/or after
fracturing as the fractures closes.
[0071] Embodiments of methods of this invention provide a proppant
placement step involving injecting alternating slugs of
proppant-free fluids and proppant-containing fluids into the
fractures of the fracturing layer above fracturing pressure through
a number of perforation groups in a wellbore, and causing the
sequences of slugs of proppant-free fluids and proppant-containing
fluids injected through at least one pair of perforation groups to
be separated by a region of injected proppant-free fluids. Again,
the slugs ofproppant-containing fluids form proppant pillars,
clusters, or islands in the fractures during fracturing and/or
after fracturing as the fractures closes.
[0072] There are many optional variations of these methods
including, without limitation, (I) varying the proppant-free fluids
in some or all of the proppant-free fluid slugs, (ii) varying the
proppant-containing fluids in some or all of the
proppant-containing fluid slugs, (iii) varying the proppant
composition in some or all of the proppant-containing fluids, (iv)
varying slug properties of some or all of the slugs, (v) varying
the sequence of slugs, (vi) varying the number of perforation
groups, (vii) varying the perforation group separations, (viii)
varying a length of some or all of the group lengths, (ix) varying
a number of perforation in some or all of the groups, or (xii)
varying other fluid properties, other slug properties, other
fracturing properties, etc.
[0073] In other variations, the methods may have a step following
the proppant placement step involving continuous introduction of a
proppant-containing fluid into the fracturing fluid, where the
proppant has an essentially uniform particle size. This following
step may include a reinforcing material, a proppant transport
material, other materials, or mixtures thereof. The fluids may be
viscosified with a polymer or with a viscoelastic surfactant. The
number of holes in each perforation group may be the same or
different. The diameter of holes in all of the groups may be the
same or different. The lengths of the perforation groups and the
spans separating the groups may be the same or different. At least
two different perforation group forming methods may be used. Some
of the groups may be produced using an underbalanced perforation
technique or an overbalanced perforation technique. The
orientations of the perforations in all of the groups relative to
the preferred fracture plane may be the same or different.
[0074] In another variation, pairs of groups that produce slug
pulses in the formation may be separated by a perforation group
having sufficiently small perforations that the proppant bridges
and proppant-free fluid enters the formation therethrough.
Generally, a number of perforation in each group is between 2 and
300; in certain embodiments, the number may be between 2 and 100.
Generally, the perforation group length between adjacent groups is
between 0.15 m and 3.0 m; in certain embodiments the group length
is from 0.30 m to 30 m. Generally, the perforation shot density is
from 1 to 30 shots per 0.3. Generally, the proppant-containing
slugs have a volume between 80 liters and 16,000 liters.
[0075] In certain embodiments, the fluid injection sequence is
determined from a mathematical model; and/or the fluid injection
sequence includes a correction for slug dispersion; and/or the
perforation pattern is determined from a mathematical model.
[0076] In other embodiments, at least one of the parameters
including slug volume, slug composition, proppant composition,
proppant size, proppant concentration, number of holes per
perforation group, perforation group length, perforation group
separation, perforation group orientation, perforation group shot
density, lengths of perforation groups, methods of perforation, is
constant along the wellbore in the fracturing layer, or increases
or decreases along the wellbore in the fracturing layer, or
alternates along the wellbore in the fracturing layer.
[0077] The methods of this invention are designed to allow proppant
pillars, clusters, or islands to form in the fractures such that
the proppant pillars do not extend across an entire dimension of
the fractures parallel to the wellbore including regions ofproppant
pillars, clusters, or islands interrupted by flow channels or
pathways between the pillars form pathways that lead to the
wellbore, i.e., the proppant pillars, clusters, or islands are
separated in a distribution in the fractures to form the flow
channels or pathways. In certain embodiments, the proppant
compositions and the proppant placement step are designed to lower
an amount of proppant needed to achieve a desired level of fracture
conductivity greater than a fracture conductivity in the absence of
the proppant pillars, clusters, or islands formed in the
fractures.
[0078] Some embodiments illustrating the invention will be
described in terms of vertical fractures in vertical wells, but are
equally applicable to fractures and wells of any orientation, as
examples horizontal fractures in vertical or deviated wells, or
vertical fractures in horizontal or deviated wells. The embodiments
will be described for one fracture, but it is to be understood that
more than one fracture may be formed at one time. Embodiments will
be described for hydrocarbon production wells, but it is to be
understood that the Invention may be used for wells for production
of other fluids, such as water or carbon dioxide, or, for example,
for injection or storage wells. The embodiments will be described
for conventional hydraulic fracturing, but it is to be understood
that embodiments of the invention also may include water fracturing
and frac packing. It should also be understood that throughout this
specification, when a concentration or amount range is described as
being useful, or suitable, or the like, it is intended that any and
every concentration or amount within the range, including the end
points, is to be considered as having been stated. Furthermore,
each numerical value should be read once as modified by the term
"about" (unless already expressly so modified) and then read again
as not to be so modified unless otherwise stated in context. For
example, "a range of from 1 to 10" is to be read as indicating each
and every possible number along the continuum between about 1 and
about 10. In other words, when a certain range is expressed, even
if only a few specific data points are explicitly identified or
referred to within the range, or even when no data points are
referred to within the range, it is to be understood that the
inventors appreciate and understand that any and all data points
within the range are to be considered to have been specified, and
that the inventors have possession of the entire range and all
points within the range.
[0079] In certain embodiments, the proppant placement in fracturing
of fracturing layers is fracturing design, where the fracturing
design including perforation pattern, fluid sequence, fluid
compositions, etc. creates a superior placement of proppant
pillars, clusters, or islands within the fractures to increase,
optimize or maximize an amount of open (void) space or flow
pathwayes in the fractures. This, in turn, ensures increased,
optimized, or maxized hydraulic conductivity of the fractures and
enhanced hydrocarbon production from a reservoir layer. The
creation and placement of (a) proppant pillars, clusters, or
islands, (b) regions of proppant pillars, clusters, or islands, (c)
flow pathways or channels, or (d) regions of flow pathways or
channels in the fractures have the advantages of producing (a)
longer (and/or higher) fractures with the same mass of proppant,
and (b) more effective fracture clean-up of fracturing fluids from
the fractures due to a greater volume of the fracture being flow
pathways.
[0080] The embodiments will be described for conventional hydraulic
fracturing, but it is to be understood that embodiments of the
invention also may include water fracturing and frac packing. It
should also be understood that throughout this specification, when
a concentration or amount range is described as being useful, or
suitable, or the like, it is intended that any and every
concentration or amount within the range, including the end points,
is to be considered as having been stated. Furthermore, each
numerical value should be read once as modified by the term "about"
(unless already expressly so modified) and then read again as not
to be so modified unless otherwise stated in context. For example,
"a range of from 1 to 10" is to be read as indicating each and
every possible number along the continuum between about 1 and about
10. In other words, when a certain range is expressed, even if only
a few specific data points are explicitly identified or referred to
within the range, or even when no data points are referred to
within the range, it is to be understood that the inventors
appreciate and understand that any and all data points within the
range are to be considered to have been specified, and that the
inventors have possession of the entire range and all points within
the range.
[0081] The perforation design is particularly effective when used
in combination with proppant slug blends engineered to minimize
slug dispersion during their transport through the hydraulic
fractured, which may be achieved through the use of the proppant
compositions, the aggregating compositions, and/or the coating
crosslinking compositions of this invention.
[0082] Generally, the fracturing operation includes a first stage
including the injection of a pad fluid into the formation (normally
proppant-free viscosified fluid), which initiates fracture
formation and furthers fracture propagation. A second stage of the
fracturing operation generally includes a number of sub-stages.
During each sub-stage, a proppant-containing fluid slug having a
given (designed or calculated) proppant composition and
concentration is pumped (called a slug sub-stage) into the
formation followed by a proppant-free fluid interval sub-stage. The
volumes of both proppant-containing fluid slugs and proppant-free
fluid slugs significantly affects hydraulic conductivity of the
fractures due to the formation and placement of proppant pillars,
clusters, or islands in the fractures. The sequence
ofproppant-containing and proppant-free fluid slugs may be repeated
the necessary number of times to achieve a desired pillar
distribution and/or placement in the fractures. A duration of each
sub-stage, the proppant composition, the proppant concentration,
and the nature of the fluid in each slug may varied or optimized to
increase, optimize or maximize proppant pillar, cluster, or island
placement resulting in increased, improved, optimized or maximized
fracture conductivity.
[0083] At the end of the treatment a heterogeneous proppant
structure may be formed in the fractures. Following fracture
closure, proppant pillars squeeze and form stable proppant
formations (pillars) between the fracture walls and prevent the
fracture from complete closure.
[0084] In the hydraulic fracturing methods of this invention for
fracturing a subterranean formation, the fracturing sequence
generally includes a first stage or "pad stage", that involves
injecting a fracturing fluid into a borehole at a sufficiently high
flow rate that it creates hydraulic fractures in the formation. The
pad stage is pumped so that the fractures will be of sufficient
dimensions to accommodate the subsequent slug including
proppant-containing fluids. The volume and viscosity of the pad may
be designed by those knowledgeable in the art of fracture design
(for example, see "Reservoir Stimulation" 3.sup.rd Ed. M. J.
Economides, K. G. Nolte, Editors, John Wiley and Sons, New York,
2000).
[0085] Water-based fracturing fluids are common, with natural or
synthetic water-soluble polymers added to increase fluid viscosity
and are used throughout the pad and subsequent propped stages.
These polymers include, but are not limited to, guar gums: (high
molecular-weight polysaccharides composed of mannose and galactose
sugars) or guar derivatives, such as hydroxypropyl guar,
carboxymethyl guar, and carboxymethylhydroxypropyl guar.
Cross-linking agents based on boron, titanium, zirconium or
aluminum complexes are typically used to increase the polymer's
effective molecular weight, making it better suited for use in
high-temperature wells.
[0086] The second stage or "proppant stage" of a fracturing
operation involves introduction into a fracturing fluid of a
proppant in the form of solid particles or granules to form a
suspension or slury. The propped stage may be divided into a
sequence of slugs of different fracturing fluids including
non-viscosified proppant-free fluids, viscosified proppant-free
fluids, non-viscosified proppant-containing fluids, or viscosified
proppant-containing fluids. The sequence may include two or more
periodically repeated sub-stages including "carrier sub-stages"
involving the injection of the proppant-free fracturing fluids, and
"proppant sub-stages" involving the injection of
proppant-containing fracturing fluids. As a result of the periodic
(but not continual) slugging of slurry containing granular propping
materials, the proppant does not completely fill the fracture.
Rather, the proppant form clusters, posts, pillars, or islands with
channels or flow pathways therebetween through which formation or
injection fluids may pass. The volumes of proppant sub-stages and
carrier sub-stages as pumped may be different. That is, the volume
of the carrier sub-stages may be larger or smaller than the volume
of the proppant sub-stages. Furthermore, the volumes of the
sub-stages may change over time. For example, a proppant sub-stage
pumped early in the treatment may be of a smaller volume than a
proppant sub-stage pumped latter in the treatment. The relative
volume of the sub-stages is selected based on how much of the
surface area of the fracture is to be supported by the proppant
clusters, pillars, columns, or islands, and how much of the
fracture area is to be open channels through which formation fluids
are free to flow.
[0087] In certain embodiments, the proppant composition in the
slugs may include reinforcing and/or consolidating materials to
increase the strength of the proppant clusters, pillars, columns,
or islands formed and to prevent their collapse during fracture
closure. Typically, the reinforcement material is added to some of
the proppant sub-stages. Additionally, the concentrations of both
proppant and the reinforcing materials may varied continuously,
periodically, or intermittently throughout the proppant stage. As
examples, the concentration of reinforcing material and/or proppant
may be different in two subsequent proppant sub-stages. It may also
be suitable or practical in some applications of the method to
introduce the reinforcing material in a continuous fashion
throughout the proppant stage, both during the carrier and proppant
sub-stages. In other words, introduction of the reinforcing
material may not be limited only to the proppant sub-stage. In
certain embodiments, the concentration of the reinforcing material
does not vary during the entire proppant stage; monotonically
increases during the proppant stage; or monotonically decreases
during the proppant stage.
[0088] Curable, or partially curable, resin-coated proppant may be
used as reinforcing and consolidating material to form proppant
clusters. The selection of the appropriate resin-coated proppant
for a particular bottom hole static temperature (BHST) and for a
particular fracturing fluid are well known to experienced workers.
In addition, organic and/or inorganic fibers may be used to
reinforce the proppant cluster. These materials may be used in
combination with resin-coated proppants or separately. These fibers
may be modified to have an adhesive coating alone, or an adhesive
coating coated by a layer of non-adhesive substance dissolvable in
the fracturing fluid as it passes through the fracture. Fibers made
of adhesive material may be used as reinforcing material, coated by
a non-adhesive substance that dissolves in the fracturing fluid as
it passes through the fracture at the subterranean temperatures.
Metallic particles are another preference for reinforcing material
and may be produced using aluminum, steel containing special
additives that reduce corrosion, and other metals and alloys. The
metallic particles may be shaped to resemble a sphere and measure
0.1-4 mm. In certain embodiments, fibers such as metallic particles
used are of an elongated shape with an aspect ratio (length to
width or diameter) of greater than 5:1, for example a length longer
than 2 mm and a diameter of 10 to 200 microns. Additionally, plates
of organic or inorganic substances, ceramics, metals or metal-based
alloys may be used as reinforcing material. These plates may be
disk or rectangle-shaped and of a length and width such that for
all materials the ratio between any two of the three dimensions is
greater than 5 to 1.
[0089] Proppant and fluid choice are also adjustable factors in the
methods of this invention. The proppant composition and fluid
compositions are chosen to increase, optimize, or maximize a
strength of proppant clusters, pillars, columns and islands within
the fractures after fracture closure. A proppant cluster should
maintain a reasonable residual thickness at the full fracture
closure stress. This ensures an increase in fluid flow through open
channels formed between the proppant clusters. In this situation,
the proppant pack permeability, as such, is not decisive for
increasing well productivity. Thus, a proppant cluster may be
created successfully using sand whose particles are too weak for
use in standard hydraulic fracturing in the formation of interest.
A proppant cluster may also be made from sand that has a very wide
particle size distribution that would not be suitable for
conventional fracturing. This is an important advantage, because
sand costs substantially less than ceramic proppant. Additionally,
destruction of sand particles during application of the fracture
closure load might improve the strength of clusters consisting of
sand granules. This can occur because the cracking/destruction of
sand proppant particles decreases the cluster porosity and
increases the proppant compactness. Sand pumped into the fracture
to create proppant clusters does not need good granulometric
properties, that is, the usually desirable narrow diameter
distribution of particles. For example, to implement the method, it
may be suitable to use 50,000 kg of sand, of which 10,000 to 15,000
kg have a diameter of particles from 0.002 to 0.1 mm, 15,000 to
30,000 kg have a diameter of particles from 0.2 to 0.6 mm, and
10,000 to 15,000 kg have a diameter of particles from 0.005 to 0.05
mm. It should be noted that about 100,000 kg of a proppant more
expensive than sand would be necessary to obtain a similar value of
hydraulic conductivity in the created fracture using the prior
(conventional) methods of hydraulic fracturing.
[0090] In certain embodiments, some or all of the proppant
sub-stages include slugs have proppant compositions including
treated proppants and some or all of the carrier sub-stages have
aggregating compositions and/or and the coating crosslinking
compositions of this invention of this invention that cause
proppant particles to conglutinate, aggregate, or agglomerate
and/or stabilize or crosslinking the proppant coatings.
[0091] In certain embodiments, the methods the fracturing operation
may include a third stage or "tail-in stage" following the second
state involving continuous introduction of an amount of proppant.
If employed, the tail-in stage of the fracturing operation
resembles a conventional fracturing treatment, in which a
continuous bed of well-sorted conventional proppant is placed in
the fracture relatively near to the wellbore. In certain
embodiments, the tail-in stage is distinguished from the second
stage by the continuous placement of a well-sorted proppant, that
is, a proppant with an essentially uniform size of particles. The
proppant strength in the tail-in stage is sufficient to prevent
proppant crushing (crumbling), when it is subjected to the stresses
that occur upon fracture closure. The role of the proppant at this
stage is to prevent fracture closure and, therefore, to provide
good fracture conductivity in proximity to the wellbore. The
proppants used in this third stage should have properties similar
to conventional proppants.
[0092] In certain embodiments, a fracturing operation design (the
number, size, and orientation of perforations and the perforation
distribution over the pay zone) includes a perforation pattern that
acts as a "slug-splitter" for a given proppant slug, even when
injection is into a single, homogeneous formation layer (that is,
even when the fracturing layer is a single, homogeneous formation
layer). The perforation pattern result in the splitting of the
proppant slugs pumped down the wellbore into a predetermined number
of separated smaller slugs within the fractures of a particular
zone. The number of proppant slugs and the corresponding completion
design may be optimized to achieve superior performance of the
created hydraulic fracture.
[0093] In certain embodiments, the methods of pumping proppant
slugs in order to create a hydraulic fracture including a network
of proppant clusters, pillars, columns or islands and flow
pathways, or a network of proppant rich regions including clusters,
pillars, columns or islands and proppant lean regions rich, where
the flow pathways separate the proppant clusters, pillars, columns
or islands and the proppant lean regions separate the proppant rich
regions. Interconnected pathways or proppant lean regions within
the proppant pack form a network of channels throughout the
fractures from its tip to the wellbore. The network of channels
results in a significant increase of the effective hydraulic
conductivity of the created hydraulic fractures. Carrier fluid
composition, proppant fluid composition, sequence of slugs, slug
properties, perforation pattern, and/or other fracturing operation
parameters may be varied to increase, optimize, or maximize
hydraulic fracture conductivity, where the perforation pattern acts
as a "slug-splitter" as described above.
[0094] It should be noted that although some embodiments are
described for the case in which the fracturing layer is a single
rock layer, it is not limited to use in single layers. The
fracturing layer may be a single pay zone made up of multiple
permeable layers. The fracturing layer may also be made up of more
than one pay zone separated by one or more impermeable or nearly
impermeable rock layers such as shale layers, and each pay zone and
each shale layer may in turn be made of multiple rock layers. In
one embodiment, each pay zone contains multiple perforation
clusters and the processes of the invention occur in more than one
pay zone in a single treatment. In other embodiments, at least one
of the pay zones is treated by the method and at least one of the
pay zones is treated conventionally, in a single fracturing
treatment. The result is more than one fracture, at least one of
which contains proppant placed heterogeneously according to the
method of the invention. In another embodiment, the fracturing
layer is made up of more than one pay zone separated by one or more
impermeable or nearly impermeable rock layers such as shale layers,
and each pay zone and each shale layer may in turn be made of
multiple rock layers, and at least one pay zone contains multiple
perforation clusters and the processes of the invention occur in at
least one pay zone in a single treatment, but the job is designed
so that a single fracture is formed in all the pay zones and in any
intervening impermeable zones. Of course, any embodiment may be
implemented more than once in one well.
[0095] Simulations conducted have shown that the number of
perforation clusters required for a given formation typically may
vary from 1 to 100, but may be as high as 300 for some the
formations. Suitable sizes of pillars depends upon a number of
factors, such as the "slug surface volume" (the product of the
slurry flow rate and the slug duration), the number of clusters,
the leak-off rate into the formation, etc. Calculations have
revealed the importance of slug duration on the overall
productivity of the heterogeneous fracture produced. Many
reservoirs may require the slug duration to span a range of, for
example, 2 to 60 sec (this corresponds to a slug surface volume of
about 80 to 16,000 liters (0.5 to 100 barrels (bbl)) given a range
of flow rates for a typical fracturing job of from 3,200 to 16,000
liters/minute (20 to 100 barrels per minute (bpm)). Other
reservoirs will require proppant slug durations (as measured in the
surface equipment) to be up to, for example, 5 min (16,000 to
79,500 liters (100 to 500 bbl) of frac fluid given a flow rate of
3,200 to 16,000 liters/minute (20-100 bpm)). And finally, for those
treatments in which part of the fracture should be covered with
proppant homogeneously, slugs may last for 10-20 minutes and
longer. Furthermore, slug duration may also vary throughout the
treatment in order to vary characteristic pillar footprints within
a single hydraulic fracture. Typical ranges of slug duration will
be the same as just detailed above. For example, a pumping schedule
may start with 1 min long slugs and finish pumping with 5 sec long
proppant slugs with 5 sec no-proppant intervals between them.
Proppant Flowback Control and Consolidation
[0096] During fracturing application, sand and proppant are pumped
in the fracture to keep it open. The proppant if not consolidated
can flow back with the produced fluid or gas which can lead to loss
of proppant pack conductivity. Also the produced proppant can erode
the production tubular, downhole and surface equipment's that can
leads to costly repairs and downtime. One embodiment of this
invention is to pump zeta altering material/chemistry of present
invention (e.g., SandAid.TM., amine component, polyvinylpyridine,
etc.) during fracturing operation to prevent the proppant flowback.
The zeta altering material coats on to the sand or proppant and
spread evenly and agglomerates the proppant. The agglomeration
strength of the material depends on many conditions such as
temperature, mineralogy of proppant, water compositions, salts
ions, drawdown rates etc. Some of these can adversely affect the
agglomeration strength and in those cases we can still see proppant
flowback. To further increase the agglomeration strength of zeta
altering material and consolidate the proppant pack, a crosslinking
agent or combination of crosslinking agents are added to stabilize,
strengthen, and/or consolidate the coatings and aggregated
proppants, where the crosslinking agents include inorganic
crosslinking agents, organic crosslinking agents, or mixtures and
combinations thereof. The crosslinking agents are designed to form
either ionic chemical bond, covalent bonds, other bonding
interactions (hydrogen bonding, electrostatic attractive forces,
etc.), or mixtures and combinations thereof to strength the
consolidated particles in proppant pack, frac pack, unconsolidated
sand, islands, clusters, and/or pillars. The strengthening of the
proppant pack, frac pack, unconsolidated sand, islands, clusters,
and/or pillars will reduce sand, fine, and/or proppant production,
and due to higher consolidation of strengthened proppant pack, frac
pack, unconsolidated sand, islands, clusters, and/or pillars, they
will support a higher drawdown rate and possible bottom hole
pressure (BHP). The crosslinked proppant pack, frac pack,
unconsolidated sand, islands, clusters, and/or pillars allow higher
operating temperatures and reduces the rate of dissolution of zeta
altering material in production fluids. The reduce dissolution rate
reduces proppant flowback for longer a period of time in comparison
to uncrosslinked proppant pack, frac pack, unconsolidated sand,
islands, clusters, and/or pillars. The crosslinked proppant pack,
frac pack, unconsolidated sand, islands, clusters, and/or pillars
also have added advantage as they increase a temperature limit of
use of the zeta altering materials of this invention to
temperatures about 400.degree. F. Some of the new materials based
on polyvinylpyridine aggregating compositions already have better
heat stability in agglomeration than amine-phosphate reaction
product aggregating compositions such as SandAid.TM..
[0097] Embodiments of this invention relate to methods for proppant
flowback control and consolidation including treating a formation,
a weakly consolidated formation, or an unconsolidated formation
with an aggregating effective amount of a zeta potential altering
or aggregating composition of this invention and a coating
crosslinking effective amount of a coating crosslinking agent,
where the aggregating effective amount is sufficient to form
partial or complete coatings on surfaces of formations, surfaces of
formation fines, proppants, or other solid materials in the
formation, where the coating changes the aggregating propensity of
the surfaces and the coating crosslinking effective amount is
sufficient to stabilize or strength the coating by forming a
crosslinked coating. Embodiments of the invention also relate to
surfaces having a crosslinked aggregating composition coating
thereon.
Sand and Fines Control and Consolidation
[0098] Sand and fines production during oil and gas production from
a well is a big problem globally. The sand and fines production
leads to frequent cleanup and treatment of the wellbore to keep
producing. Also fines and sand production can erode the production
tubular, downhole and surface pumps and equipment's that can leads
to costly repairs and downtime. The second embodiment of this
invention is to treat the formation with zeta altering
material/chemistry of present invention (e.g., amine-phosphate
reaction product, polyvinylpyridine, polyenamines, etc.) to reduce
or prevent sand and fines production. The zeta altering materials
coat fines, sand and/or proppants and spread evenly over the
surfaces altering the agglomeration properties of the fines, sand,
and/or proppant. The aggregation reduces or prevents fines
migration as well as production of sand thus eliminating or
reducing frequent cleanup or workover of the well. The
agglomeration strength of the zeta altering material depends on
many conditions such as temperature, mineralogy ofproppant, water
compositions, salts ions, drawdown rates etc. Some of these may
adversely affect the agglomeration strength and in those cases,
sand and/or fines production may occur. To further increase the
agglomeration strength of zeta altering material and consolidate
the sand or formation, organic crosslinking agents, inorganic
crosslinking agents, or mixtures and combinations thereof are added
to the coating to increase strength, hardness, stability, and
consolidation. The improved strength, hardness, stability, and
consolidation reduces or prevents sand and fines production and
permits higher drawdown rates. The crosslinking also makes the
material work at higher temperatures and reduces the rate of
dissolution of the material in the production fluids. The reduce
dissolution rate reduces or prevents sand and fines production for
a longer period of time. The method may be used in open hole and
cavities, cased and perforated wells, screens, slotted liners,
expandable screens, cased hole gravel pack, open hole gravel pack,
high rate water packs and tip screen, fracturing out
fracturing.
[0099] Embodiments of this invention relate to methods for sand and
fines control and consolidation including treating a formation, a
weakly consolidated formation, or an unconsolidated formation with
an aggregating effective amount of a zeta potential altering or
aggregating composition of this invention and a coating
crosslinking effective amount of a coating crosslinking agent,
where the aggregating effective amount is sufficient to form
partial or complete coatings on surfaces of formations, surfaces of
formation fines, sand, or other solid materials in the formation,
where the coating changes the aggregating propensity of the
surfaces and the coating crosslinking effective amount is
sufficient to stabilize or strength the coating by forming a
crosslinked coating. Embodiments of the invention also relate to
surfaces having a crosslinked aggregating composition coating
thereon.
Treatment Through Screens
[0100] In other embodiments, the zeta altering compositions of the
present invention may be used with sand screens to improve sand and
fines control, reducing sand and fines migration into the producing
fluids. Generally sand screens are employed to control sand and
fines co-production, but overtime the screens become plugged by
fines migrating from the formation towards the production tubing.
Once plugged, the screen are generally treated with acid or
solvents to clean them, where the treatments may be frequent. If
after installation of the screen, the formation is treated with
zeta altering compositions of the present invention, then the
screens will have improved sand and fine control reducing or
preventing fines migration and the screens will last longer without
the need for clean out operations. Also the near well bore area may
be consolidated with the crosslinked zeta altering compositions of
this invention to reduce or prevent sand production.
[0101] Embodiments of this invention relate to methods for treating
through screens including treating a formation, a weakly
consolidated formation, or an unconsolidated formation through
production screen with an aggregating effective amount of a zeta
potential altering or aggregating composition of this invention and
a coating crosslinking effective amount of a coating crosslinking
agent, where the aggregating effective amount is sufficient to form
partial or complete coatings on surfaces of formations, surfaces of
formation fines, proppant sand, or other solid materials in the
formation, where the coating changes the aggregating propensity of
the surfaces and the coating crosslinking effective amount is
sufficient to stabilize or strength the coating by forming a
crosslinked coating. Embodiments of the invention also relate to
surfaces having a crosslinked aggregating composition coating
thereon.
Coated Proppant
[0102] During fracturing, resin coated proppants may be used to: a)
reduce diagenisis of proppant and prevent precipitate formation in
pores that plug the pores lower formation permeability, allowing
conductivity to decline more slowly compared to uncoated proppant,
b) to reduce proppant crushing under formation pressure and
generating fines, e.g., resin coated proppant keep fines in the
pack and reduce or prevent fines migration through proppant pack
and conductivity impairment, c) aggregate or fuse the coated
proppant under stress and heat reducing or preventing flowback of
proppant during production, and/or d) reduce proppant interaction
with other fluid additives. However, resin coated proppant are
generally only produced in plant or manufacturing facilities at
considerable cost. Embodiments of this invention relate to methods
for generating resin coated proppants using zeta altering
compositions to partially or completely coat the proppant and
crosslinking compositions to strength, strengthen, and/or stability
the coated proppants and/or aggregates of the coated proppants. The
coated proppant of the present invention may be produced in
manufacturing facilities, on site, and/or downhole.
Coated Proppant Manufacturing Processes
[0103] Embodiments of this invention relate to methods for
manufacturing coated proppants including the step of contacting a
proppant and a zeta altering composition of this invention with
stirring or mixing. The stirring or mixing may be achieved in
stirred tank reactors, mixing tanks with augers, rolling tanks, or
other mixing reactors in a manufacturing facility. The contacting
continues for a time sufficient for the zeta altering composition
to partially or completely coat the proppant. The Zeta altering
compositions are liquids and when contacted with sand or proppant
with or without a mixing aid, will form a partial or complete thin
film on the surface of the proppant. In other embodiments, the zeta
altering composition is dropped on to proppant to coat it. The
coating is soft enough and allows the bed to be mixed and stirred.
To make the coating hard, a crosslinking composition including
organic crosslinking agents, inorganic crosslinking agents, or
mixtures and combinations thereof may be pumping or injected as an
aqueous metal salt solution into the coated proppant with stirring.
The material may then be washed with water to obtain hard coated
proppant, which may then be pumped downhole during fracturing, frac
pack, or gravel pack operations.
[0104] In other embodiments, coated proppant may also be prepared
by including the organic crosslinking agents into zeta altering
material before coating of the proppant. After coating, the
material is subjected to heat to strengthen the coating on the
proppant.
[0105] In other embodiments, soft coated proppant may also be added
to a fracturing, frac pack, or gravel pack fluid, and then a
crosslinking composition including organic crosslinking agents,
inorganic crosslinking agents, or mixtures and combinations thereof
are added into the fluid to crosslink the soft coated proppant as
the fluid proceeds downhole to form strengthen coated proppant
downhole at a controlled rate as the proppant is forced into
fractures created in the formation during fracturing.
[0106] In other embodiments, the proppant may be produced by adding
a zeta altering composition to the fluid including proppant in an
amount sufficient to form partially and/or completely coated
proppants either at the surface or as the fluid proceeds downhole
or as the proppant is forced into the formation during fracturing.
In certain embodiments, a crosslinking composition of this
invention may be added to the fluid either concurrently with the
zeta altering composition on the surface, as the fluid proceeds
down hole, or as the fluid enters the formation, after the zeta
altering composition additions at the surface, as the fluid
proceeds down hole, or as the fluid enters the formation, and/or
after proppant placement in formation. The strengthening may occur
upon contact or may occur after heating on the surface, as the
fluid proceeds downhole, as the fluid proceeds into the formation,
or as the proppant is placed in the formation.
Consolidating Near Well Bore in Proppant Pack and Fracturing
[0107] Other embodiments of the present invention relate to methods
including coating proppant with a zeta altering composition of
present invention to form a coated proppant pack during fracturing
or remedial treatment for proppant flowback control. The zeta
altering compositions are then crosslinked by a crosslinking
compositions of this invention to consolidate the proppant pack
near the well bore leaving the far well bore material
uncrosslinked. The consolidated portion will reduce or prevent any
sand production as it has strong consolidation or strength. The
zeta altering composition which is not consolidated will help in
prevention of fines migration from the formation by locking them
effectively. Crosslinking all the coating will result in a loss of
fines control activity, which will be detrimental for the proppant
pack. The crosslinked coated proppant is designed to have both good
consolidation strength as well as fines control ability.
Consolidating Near Well Bore in Remedial Sand and Fines Control
[0108] Other embodiments for sand and fines control relate to
methods includes treating the formation with a zeta altering
composition of present invention and then consolidating a near well
bore portion by treating the formation with a crosslinking
compositions leaving far well bore material uncrosslinked. The near
well bore consolidation will reduce or prevent sand production of
cave in of the open hole whereas the material far into the
formation will reduce or prevent the fines migration by
agglomeration with zeta altering composition.
Coal Bed Consolidation to Prevent Coal Fines Migration
[0109] During coal bed methane production, fines from coal pieces
migrate and plug the pores and impede gas production. In another
embodiment, the coal fines can be agglomerated in coal bed methane
production by zeta potential altering chemistry of the present
invention. The zeta altering material can be used to treat the coal
bed by pumping the material in brine, water or frac fluid (linear
or crosslinked). The treated bed can further be consolidated by
adding a crosslinking composition of this invention, where the
crosslinking composition is an aqueous solution will crosslink the
zeta altering composition of the present invention when treated
area will be washed with this solution. Once the material is pumped
in the formation the organic crosslinker will get activated by the
heat and will crosslink the zeta altering material and consolidate
the coal bed. This method will enhance wormhole and cavity
stability and as such will enhance CBM wells.
Equalizing Permeability of Formation by Forming Degradable Filter
Cakes and Treating with Zeta Altering Chemistry
[0110] The present invention also relates to further consolidate
formation treated with an aggregating compositions by further
treating the filter cake with an aggregating crosslinking
composition of this invention so that filter cake reduces or
prevents fines and sand production or improve fines and sand
control. The crosslinking may be performed by pumping a
crosslinking composition into the well after the filter cake has
been formed and after treatment with the aggregating
composition.
Treating Formation in Horizontal or Vertical Wells
[0111] Zeta altering material is injected with the treating fluid
and proppant. The coating crosslinking compositions in water or
brine treatment fluids may be pumped at the tail end to crosslink
the zeta altering material coating. Organic crosslinkers may also
be mixed with zeta altering material before being pumped with the
fluid and proppant.
Remedial Treatment
[0112] Injected with fluids mentioned below. Metal crosslinking
ions in water, brine of treatment fluids can be pumped at the tail
end to crosslink the zeta altering material. Organic crosslinkers
can be mixed with zeta altering material before they are pumped
with the fluid and proppant.
Chemical Sand Control
[0113] Embodiments of the methods and systems of this invention
relate to sand control, where an effective amount of an
aggregation, agglomeration or conglomeration composition with or
with aggregation stabilizing and/or strengthening compositions is
injected into a producible formation or a zone thereof, where the
composition alters an aggregation potential and/or a zeta potential
of formation surfaces and/or formation particulate to chemically
enhance particular aggregation, agglomeration or conglomeration
within the formation or zone thereof and the crosslinking
compositions strengthens the treated particulate and, thereby,
reduce, substantially eliminate or eliminate co-production of
formation particulate. The method includes placing an effective
amount of the aggregation, agglomeration or conglomeration
composition into an existing down hole producible formation or zone
causing formation particulate to bind together and/or to bind to
formation surfaces to form a conglomerated formation or zone
thereof. After the conglomeration, the conglomerated formation can
produce hydrocarbons and/or liquids at a higher substantially sand
free rate and/or a higher sand free rate, thus, maximizing sand
free production rates of the formation or zone. The composition can
be injected into the formation or zone thereof using existing
production tubing, liners or equipments or using a specially
designed work string. Of course, the treatment can be directed into
a plurality of zones of a producible formation, into a long
interval of the formation or into the entire formation depending on
the desired result to be achieved.
Enhanced Gravel or Fracture Packing
[0114] Embodiments of the methods and systems of this invention
relate for gravel and/or fracture packing producible formations or
zones therein, where the methods or systems include pre-treating,
in-situ treating, and/or post treating the formation or zones
thereof to enhance sand control or reduce formation particulate
co-production of well undergoing a gravel packing and/or fracture
packing operations. The treatment involves injecting into the
formation or zones thereof, an effective amount of an aggregating,
agglomerating or conglomerating composition with or with
aggregation stabilizing and/or strengthening compositions
sufficient to alter an aggregation potential and/or zeta potential
of the formation or zone surfaces and formation particulate
resulting in a reduction, substantial elimination or elimination of
the co-production of formation particulate including sand, grains
and/or fines. Gravel packing is a sand-control method used to
prevent production of formation sand. In gravel pack operations, a
steel screen is placed in the wellbore and the surrounding annulus
packed with prepared gravel of a specific size designed to prevent
the passage of formation particulate through the introduced gravel
pack. The introduction of the prepared gravel results in a
stabilization of the formation or zone thereof, while causing
minimal impairment to well productivity. Fracture packing is a
productivity enhancing operation, where a producible formation is
fractured under pressure. During or after fracturing, a fluid
including a proppant and generally a consolidation composition is
injected into the formation to hold open the fractures permitting
enhanced production. Traditional gravel packing and fracture
packing, although useful in reducing formation particulate
co-production, the migration of formation particulate is not fully
inhibited and screen plugging and down stream equipment damage can
still occur. However, such formation particulate co-production can
be reduced, substantially eliminated or eliminated by treating with
the conglomeration compositions of this invention before, during or
after either gravel packing or fracture packing.
Enhance Expandable Screen Function in Open Hole
[0115] Embodiments of the methods and systems of this invention
relate to methods and systems to enhance formation particulate
co-production in completion operation involving the use of
expandable screens in open hole wells. The method involve
pre-treating, in-situ treating and/or post treating of a producible
formation, an interval within the formation or zones within the
formation with an effective amount of an aggregating, agglomerating
or conglomerating composition with or with aggregation stabilizing
and/or strengthening compositions sufficient to alter an
aggregation potential and/or zeta potential of the formation or
zone surfaces and formation particulate resulting in a reduction,
substantial elimination or elimination of the co-production of
formation particulate including sand, grains and/or fines. The
reduction, substantial elimination or elimination of the
co-production of formation particulate reduces screen plugging
increasing screen lifetime and production lifetime at the same or
higher relative draw down pressure.
Enhance Expandable Screen Function in Cased Hole
[0116] Embodiments of the methods and systems of this invention
relate to methods and systems to enhance formation particulate
co-production in completion operation involving the use of
expandable screens in cased hole wells. The method involve
pre-treating, in-situ treating and/or post treating of a producible
formation, an interval within the formation or zones within the
formation with an effective amount of an aggregating, agglomerating
or conglomerating composition with or with aggregation stabilizing
and/or strengthening compositions sufficient to alter an
aggregation potential and/or zeta potential of the formation or
zone surfaces and formation particulate resulting in a reduction,
substantial elimination or elimination of the co-production of
formation particulate including sand, grains and/or fines. The
reduction, substantial elimination or elimination of the
co-production of formation particulate reduces screen plugging
increasing screen lifetime and production lifetime at the same or
higher relative draw down pressure.
Enhance Stand Alone Screen Function in Open Hole
[0117] Embodiments of the methods and systems of this invention
relate to methods and systems to enhance formation particulate
co-production in completion operation involving the use of stand
alone screens in open hole wells. The method involve pre-treating,
in-situ treating and/or post treating of a producible formation, an
interval within the formation or zones within the formation with an
effective amount of an aggregating, agglomerating or conglomerating
composition with or with aggregation stabilizing and/or
strengthening compositions sufficient to alter an aggregation
potential and/or zeta potential of the formation or zone surfaces
and formation particulate resulting in a reduction, substantial
elimination or elimination of the co-production of formation
particulate including sand, grains and/or fines. The reduction,
substantial elimination or elimination of the co-production of
formation particulate reduces screen plugging increasing screen
lifetime and production lifetime at the same or higher relative
draw down pressure.
Enhance Stand Alone Screen Function in Cased Hole
[0118] Embodiments of the methods and systems of this invention
relate to methods and systems to enhance formation particulate
co-production in completion operation involving the use of stand
alone screens in cased hole wells. The method involve pre-treating,
in-situ treating and/or post treating of a producible formation, an
interval within the formation or zones within the formation with an
effective amount of an aggregating, agglomerating or conglomerating
composition with or with aggregation stabilizing and/or
strengthening compositions sufficient to alter an aggregation
potential and/or zeta potential of the formation or zone surfaces
and formation particulate resulting in a reduction, substantial
elimination or elimination of the co-production of formation
particulate including sand, grains and/or fines. The reduction,
substantial elimination or elimination of the co-production of
formation particulate reduces screen plugging increasing screen
lifetime and production lifetime at the same or higher relative
draw down pressure.
Systems and Methods for Well Completion
[0119] Embodiments of systems and methods of this invention relate
to running a working string into a well including a producible
formation or zone, where the working sting comprises a combination
of jointed pipes and a selection of perforating gun(s), injection
packer(s) and/or circulation control valve(s) to direct placement
of an effective amount of an aggregating, agglomerating or
conglomerating composition with or with aggregation stabilizing
and/or strengthening compositions into a formation, where the
effective amount is sufficient to alter an aggregation potential
and/or zeta potential of the formation or zone surfaces and
formation particulate resulting in a reduction, substantial
elimination or elimination of the co-production of formation
particulate including sand, grains and/or fines with or without
pre- or post flush.
[0120] Embodiments of systems and methods of this invention relate
to running coiled tubing into a well including a producible
formation or zone, where the coiled tubing comprises a plurality of
perforating gun(s), injection packer(s) and circulation control
valve(s) to direct placement of an effective amount of an
aggregating, agglomerating or conglomerating composition with or
with aggregation stabilizing and/or strengthening compositions into
a formation, where the effective amount is sufficient to alter an
aggregation potential and/or zeta potential of the formation or
zone surfaces and formation particulate resulting in a reduction,
substantial elimination or elimination of the co-production of
formation particulate including sand, grains and/or fines with or
without pre- or post flush.
[0121] Embodiments of systems and methods of this invention relate
to running coiled tubing into a well including a producible
formation or zone in combination with one or a plurality of down
hole tools to direct placement of an effective amount of an
aggregating, agglomerating or conglomerating composition with or
with aggregation stabilizing and/or strengthening compositions into
a formation, where the effective amount is sufficient to alter an
aggregation potential and/or zeta potential of the formation or
zone surfaces and formation particulate resulting in a reduction,
substantial elimination or elimination of the co-production of
formation particulate including sand, grains and/or fines with or
without pre- or post flush.
[0122] Embodiments of systems and methods of this invention relate
to treating a well with an effective amount of an aggregating,
agglomerating or conglomerating composition with or with
aggregation stabilizing and/or strengthening compositions into a
formation, where the effective amount is sufficient to alter an
aggregation potential and/or zeta potential of the formation or
zone surfaces and formation particulate resulting in a reduction,
substantial elimination or elimination of the co-production of
formation particulate including sand, grains and/or fines through
existing production tubing.
[0123] Embodiments of systems and methods of this invention relate
to completing a well into a producible formation or zone, by
displacing the drilling fluid before, during or after drilling into
the producible formation or zone with an effective amount of an
aggregating, agglomerating or conglomerating composition with or
with aggregation stabilizing and/or strengthening compositions into
a formation, where the effective amount is sufficient to alter an
aggregation potential and/or zeta potential of the formation or
zone surfaces and formation particulate resulting in a reduction,
substantial elimination or elimination of the co-production of
formation particulate including sand, grains and/or fines.
Slug Sequencing and Heterogeneous Proppant Placement
[0124] Various software tools are commercially available for
fracture modeling tool, either as licensable modules or as part of
an overall fracturing system, such as, for example, the hydraulic
fracturing design and evaluation engineering application available
from Schlumberger Oilfield Services under the trade designation
FRACCADE, which is available in an integrated suite of engineering
applications for well construction, production and intervention
available under the trade designation CADE OFFICE. For example, the
FRACCADE modeling tool is available with: a closure
test/calibration module under the trade designation DATAFRAC; a PSG
module; an APM module; an optimization sub-module; a P3D simulator;
an acid fracturing simulator; a multi-layered fracture sub-module;
and so on; that can be used in an heterogeneous proppant placement
(HPP) job or can be appropriately modified by the skilled artisan
for use in an HPP job. For example, the PSG module may be modified
with a dispersion algorithm to produce a pulsated proppant pumping
schedule.
[0125] The design and updating of the model can include determining
the amount of proppant for delivery. For example, an initial model
can solve an optimization problem to determine the amount of
proppant to be used to achieve particular fracture dimension.
Results from the solved problem can then be used to develop an
initial proppant placement schedule. As used herein, the term
"proppant placement schedule" refers to a schedule for placing the
proppant in the fracture and can include a pumping schedule, a
perforation strategy, and the like or a combination thereof. A
pumping schedule is a plan prepared to specify the sequence, type,
content and volume of fluids to be pumped during a specific
treatment. A perforation strategy is a plan to direct the flow of a
well treatment fluid through certain perforations in a wellbore
casing and/or to inhibit flow through other perforations and can
include, for example, plugging and/or opening existing perforations
or making new perforations to enhance conductivity and to control
fracture growth.
[0126] The proppant placement schedule can include varying a
proppant concentration profile in the treatment fluid. Further, the
proppant concentration profile can be varied according to a
dispersion method. For example, the model can include process
control algorithms which can be implemented to vary surface
proppant concentration profile to deliver a particular proppant
slug concentration profile at perforation intervals. Under a normal
pumping process, a slug of proppant injected into a wellbore will
undergo dispersion and stretch and loose "sharpness" of the
proppant concentration at the leading and tail edges of the
proppant slug. For a uniform proppant concentration profile, the
surface concentration profile can be solved by inverting a solution
to a slug dispersion problem. Dispersion can thus be a mechanism
which "corrects" the slug concentration profile from an initial
surface value to a particular downhole profile.
[0127] With reference to E. L. Cussler, Diffusion: Mass Transfer in
Fluid Systems, Cambridge University Press, pp. 89-93 (1984), an
example of a system of equations that can be solved is shown below
for a Taylor dispersion problem--laminar flow of a Newtonian fluid
in a tube, where a solution is dilute, and mass transport is by
radial diffusion and axial convection only. Virtually any fluid
mechanics problem can be substituted for the above system,
including turbulent or laminar flow, Newtonian or non-Newtonian
fluids and fluids with or without particles. In practice, a
downhole concentration profile will be defined, and equations
solved in the inverse manner to determine initial conditions, for
example, rates of addition for proppant, to achieve particular
downhole slug properties.
[0128] The equations can include, for example,
c _ 1 = M .pi. R 0 2 4 .pi. E z t e - ( z - v 0 t ) 2 / 4 E 2 t
##EQU00001##
where M is total solute in a pulse (the material whose
concentration is to be defined at a specific downhole location),
R.sub.0 is the radius of a tube through which a slug is traveling,
z is the distance along the tube, .nu..sup.O is the fluid's
velocity, and t is time. A dispersion coefficient Ez can be shown
to be,
E = ( R 0 v 0 ) 2 48 D ##EQU00002##
where D is a diffusion coefficient. A system of equations that
yield this solution follows. Variable definitions can be found in
E. L. Cussler, Diffusion: Mass Transfer in Fluid Systems, Cambridge
University Press, pp. 89-93 (1984).
.differential. c _ 1 .differential. .tau. = ( v 0 R 0 48 D )
.differential. 2 c _ 1 .differential. .zeta. 2 ##EQU00003##
subject to the conditions,
.tau. = 0 , all .zeta. , c _ 1 = M .pi. R 0 2 .delta. ( .zeta. )
##EQU00004## .tau. > 0 , .zeta. = .+-. .infin. , c _ 1 = 0
##EQU00004.2## .tau. > 0 , .zeta. = 0 , .delta. c _ 1 .delta.
.tau. ##EQU00004.3##
[0129] The system of equations above can be applied in general to
design any downhole proppant concentration profile, slugged or
continuous. The solution for a dispersion of granular material flow
in a fluid down a wellbore can be inverted to calculate a
corresponding surface concentration of proppant in the fracturing
fluid. Process control technology can then take this surface
concentration schedule and proportion the proppant accordingly. For
example, the surface concentration schedule can be factored into
the model, the proppant placement schedule adjusted to the model
and proppant delivered according to the proppant placement
schedule.
[0130] The pumping time of"no slug", for example when the
proppant-lean fluid is pumped, is one of the key parameters in an
HPP proppant placement schedule. The "no slug" parameter can
control the distance between columns of pillars created in the
fracture. A "no slug" time which is too high can result in a
pinching point, an area in which the fracture is at least partially
collapsed due to a lack of support between two columns of pillars.
A pinch point, or pinching, can block fracture conductivity and,
therefore, effect production.
[0131] Another example of a computer software suite for performing
heterogeneous proppant placement is found in U.S. Pat. No.
7,451,812 issued 18 Nov. 2008, but any protocol of slug injection,
slug sequencing, and slug alternation may be used to produce and/or
improve proppant island placement.
[0132] In a first order approximation the distance, L, between two
neighboring columns of pillars in the fracture can be calculated by
the following dependence relation:
L = t noslug Q rate 2 w frac H frac ##EQU00005##
where t.sub.noslug is the pumping time during which no proppant is
pumped, Q.sub.rate is the pump flowrate, w.sub.frac is the fracture
width and H.sub.frac is the fracture height. The numerator thus
includes the total volume of the no-proppant slug. In the
denominator, a factor of 2 accounts for two fracture wings.
[0133] Pinching can occur whenever the distance L is smaller than a
critical value, L.sub.crit, wherein:
L = t noslug Q rate 2 w frac H frac ##EQU00006##
[0134] The two parameters in the numerator on the right side of the
above equation can be controlled during treatment, while the two in
the denominator are not controlled and can change during
treatment.
[0135] The consequences of pinching can be dramatic. Overall
fracture conductivity can be considered as a chain of hydraulic
conductivities of different parts of the fracture. Thus, the
overall conductivity can be governed by the conductivity of a
less-conducted fracture part. In the case of pinching, the fracture
conductivity can be equal to the conductivity of the area where
pinching occurred.
[0136] A simplified equation can be used to calculate fracture
conductivity. The fracture conductivity is proportional to the
third power of fracture width
k.about.w.sup.3
where k is the fracture conductivity and w is the fracture
width.
[0137] In a pinching area, fracture width can be of the order of
0.05 mm or less, with this width due to the natural roughness of
the fracture walls. In extreme cases where there is little to no
wall roughness, the fracture width is essentially equal to zero
(0), as is the effective fracture conductivity.
[0138] The mechanical properties of the pillars expected to form
and of the formation such as, for example, Young's modulus,
Poisson's ratio, formation effective stress, and the like can have
a large impact on the fracture modeling and treatment design. For
example, an optimization problem according to the formation
mechanical properties can be solved during the design of an initial
model to maximize the open channel volume within a fracture.
[0139] Young's modulus refers to an elastic constant which is the
ratio of longitudinal stress to longitudinal strain and is
symbolized by E. It can be expressed mathematically as follows:
E=(F/A)/(.DELTA.L/L), where E=Young's modulus, F=force, A=area,
.DELTA.L=change in length, and L=original area.
[0140] Poisson's ratio is an elastic constant which is a measure of
the compressibility of material perpendicular to applied stress, or
the ratio of latitudinal to longitudinal strain. Poisson's ratio
can be expressed in terms of properties that can be measured in the
field, including velocities of P-waves and S-waves as follows:
s=1/2(V.sub.p2-2V.sub.s.sup.2)/(V.sub.p2-V.sub.s.sup.2), where
s=Poisson's ratio, V.sub.p=P-wave velocity and V.sub.s=S-wave
velocity. Effective stress, also know as "effective pressure" or
"intergranular pressure", refers to the average normal force per
unit area transmitted directly from particle to particle of a rock
or soil mass.
[0141] Scheduling and placement of the proppant during the HPP
hydraulic fracture treatment can be different than traditional
treatments. In HPP treatments, slugging the proppant can aid in
correctly placing clusters in various locations in the fracture.
For example, the proppant placement schedule can include slugs of
proppant alternated with a proppant-lean fluid, for example "no
slug" fluids, as illustrated in the HPP examples of FIGS. 1A-D
wherein the alternating proppant slug and proppant-lean fluid
technique is compared with the techniques of continuously
increasing proppant injection and step change proppant injection,
respectively. Proppant-lean fluids can include fluids with some
concentration of proppant, though the concentration of proppant in
the proppant-lean fluid is less than the concentration of proppant
in the proppant slug.
[0142] Heterogeneous proppant placement for open channels in a
proppant pack can be achieved by applying techniques such as
addition of a heterogeneity trigger to the treatment fluid while
pumping. The treatment fluid can include a chemical reactant
heterogeneity trigger, a physical heterogeneity trigger such as
fibers or a combination thereof. In some treatments, a trigger may
be added periodically.
[0143] Embodiments of the present invention relate to re-healable
proppant islands that comprise a first amount of a treated proppant
and a second amount of a crosslink treated proppant, where the
treated proppant comprises a proppant having a partial or complete
coating of a zeta potential altering composition and where the
crosslink treated proppant comprises a crosslinked zeta potential
altering composition coated proppant. The first and second amounts
are sufficient: (a) to allow formation of proppant islands in
fractures formed in a formation or zone thereof during fracturing
operations and to maintain the proppant islands substantially
intact, if the proppant islands and/or particles within the
proppant islands move within the formation during and/or after
fracturing operations, or during injection operations, or during
production operations, or (b) to allow formation of proppant
islands in fractures formed in a formation or zone thereof during
fracturing operations, to allow the proppant islands to re-heal or
break apart and reform during and/or after fracturing operations,
or during injection operations, or during production operations
maintaining high fracture conductivity, and to capture formation
fines during and/or after fracturing operations, or during
injection operations, or during production operations. In other
embodiments, the islands may further include a third amount
untreated proppant, a fourth amount of a non-erodiblel fiber, and a
fifth amount of an erodible material comprising erodible particles,
erodible fibers, or mixtures and combinations thereof. In other
embodiments, the zeta potential altering composition comprises an
aggregating composition comprising an amine-phosphate reaction
product, an amine component, an amine-phosphate reaction product,
amine polymeric aggregating composition, a coacervate aggregating
composition, or mixtures and combinations thereof. In other
embodiments, the coating crosslinking composition comprising
inorganic crosslinking agents, organic crosslinking agents, or
mixtures and combinations thereof.
[0144] Embodiments of this invention relate to self healing
proppant islands that comprise a first amount of a treated proppant
and a second amount of a crosslink treated proppant, where the
treated proppant comprises a proppant having a partial or complete
coating of a zeta potential altering composition and where the
crosslink treated proppant comprises a crosslinked zeta potential
altering composition coated proppant, where the first and second
amounts are sufficient: (a) to allow formation of proppant islands
in fractures formed in a formation or zone thereof and to allow the
islands to break apart and reform without substantial loss in
proppant during and/or after fracturing operations, or during
injection operations, or during production operations, or (b) to
allow formation of proppant islands in fractures formed in a
formation or zone thereof, to allow the islands to break apart and
reform without substantial loss in proppant during and/or after
fracturing operations, or during injection operations, or during
production operations, and to capture formation fines during and/or
after fracturing operations, or during injection operations, or
during production operations. In certain embodiments, the islands
further comprise a third amount untreated proppant, a fourth amount
of a non-erodible fiber, and a fifth amount of an erodible material
comprising erodible particles, erodible fibers, or mixtures and
combinations thereof, where the relative amounts of the different
type of proppant materials and fibers are chosen to fit particular
features of a formation to be fractured. In other embodiments, the
zeta potential altering composition comprises an aggregating
composition comprising an amine-phosphate reaction product, an
amine component, an amine-phosphate reaction product, amine
polymeric aggregating composition, a coacervate aggregating
composition, or mixtures and combinations thereof. In other
embodiments, the coating crosslinking composition comprising
inorganic crosslinking agents, organic crosslinking agents, or
mixtures and combinations thereof.
[0145] Embodiments of this invention relate to compositions for
forming proppants islands within a formation or zone thereof, where
the composition comprises a first amount of a treated proppant and
a second amount of a crosslink treated proppant, where the treated
proppant comprises a proppant having a partial or complete coating
of a zeta potential altering composition and where the crosslink
treated proppant comprises a crosslinked zeta potential altering
composition coated proppant, where the first and second amounts are
sufficient: (a) to allow the compositions to form islands in the
formation or zone thereof during and/or after fracturing
operations, or (b) to allow the compositions to form islands in the
formation or zone thereof and to capture formation fines during
and/or after fracturing operations, or during injection operations,
or during production operations. In certain embodiments, the
islands further comprise a third amount untreated proppant, a
fourth amount of a non-erodible fiber, and a fifth amount of an
erodible material comprising erodible particles, erodible fibers,
or mixtures and combinations thereof. In other embodiments, the
zeta potential altering composition comprises an aggregating
composition comprising an amine-phosphate reaction product, an
amine component, an amine-phosphate reaction product, amine
polymeric aggregating composition, a coacervate aggregating
composition, or mixtures and combinations thereof. In other
embodiments, the coating crosslinking composition comprising
inorganic crosslinking agents, organic crosslinking agents, or
mixtures and combinations thereof.
[0146] Embodiments of this invention relate to systems for forming
proppant pillars in a formation during formation fracturing
comprising the steps of a sequence of injections of a plurality of
different fracturing fluids, where the different fracturing fluids
selected from the groups consisting of: (a) proppant-free fluids
including (i) a base fluid or (ii) a base fluid and an aggregating
composition, a coating crossslinking composition, and/or a
viscosifying composition and (b) proppant-containing fluids
including (i) a base fluid, a viscosifying composition, and a
proppant composition or (ii) a base fluid, a viscosifying
composition, a proppant composition, an aggregating composition
and/or a coating crossslinking composition. In certain embodiments,
the sequences may include single injections of each fluid in any
order or multiple injections of each fluid in any order. In other
embodiments, the sequence may include a plurality of first fluid
injections, a plurality of second fluid injections, and a plurality
of third fluid injections. In other embodiments, the sequence may
include single injections of the first, second, and third fluids
repeated a number of times, where the number of times extends over
the entire proppant placement stage of the fracturing operation. In
other embodiments, the sequence may include multiple injections of
each fluid in any given order. In other embodiments, the sequence
may also include a hold period between each injection.
[0147] In other embodiments, the sequence may include a first fluid
injection, a first hold time, a second fluid injection, a second
hold time, and a third fluid injection, and a third hold time,
where the first, second and third fluid may be any of the fluid
compositions listed above.
[0148] Embodiments of this invention relate to methods for
fracturing including a pad stage comprising injecting into a
formation a pad fluid into a formation under fracturing conditions
to fracture and/or extend fractures. The methods also include a
proppant placement stage comprising injecting a series ofproppant
stages fluids according to a sequence designed to form proppant
pillars or islands in the fractures. The proppant stage fluids
include at least one proppant-free fluid and at least one
proppant-containing fluid. The proppant-free fluids include
viscosified fluids with or without an aggregating composition
and/or with or without a coating crossslinking composition, and
crosslinked viscosified fluids with or without an aggregating
composition and/or with or without a coating crossslinking
composition. The proppant-containing fluids include viscosified
fluids including a proppant compositions with or without an
aggregating composition and/or with or without a coating
crossslinking composition, a crosslinked fluid including a proppant
composition with or without an aggregating composition and/or with
or without a coating crossslinking composition. The methods may
also include a tail-in stage comprising injecting in a tail-in
fluid. The proppant stage may include the sequential injection of
thousands of slugs of proppant-free and proppant-containing fluids,
where the slug pulses have a duration between 5 s and 30 s.
[0149] Embodiments of this invention relate to methods for
fracturing a subterranean formation comprising a proppant placement
stage comprising injecting into the formation penetrated by a
wellbore at least two fracturing fluids differing in: (1) at least
one proppant composition property, or (2) at least one fracturing
fluid property, or (3) a combination of these differences, where
the differences improve proppant placement and proppant island
formation in the fractures. In certain embodiments, the fracturing
fluid properties include fluid composition, fluid pressure, fluid
temperature, fluid pulse duration, proppant settling rate, or
mixtures and combinations thereof, and the proppant composition
properties include proppant types, proppant sizes, proppant
strengths, proppant shapes, or mixtures and combinations thereof.
In other embodiments, the fracturing fluids are selected from the
group consisting of (a) proppant-free fluids including (i) a base
fluid or (ii) a base fluid and an aggregating composition and/or a
coating crossslinking composition and/or a viscosifying composition
and (b) proppant-containing fluids including (i) a base fluid, a
viscosifying composition, and a proppant composition or (ii) a base
fluid, a viscosifying composition, a proppant composition and an
aggregating composition and/or a coating crossslinking composition.
In other embodiments, the aggregating composition comprising an
amine-phosphate reaction product, amine component, amine polymeric
aggregating composition, a coacervate aggregating composition, or
mixtures and combinations thereof. In other embodiments, the
coating crosslinking composition comprising inorganic crosslinking
agents, organic crosslinking agents, or mixtures and combinations
thereof. In other embodiments, the proppant composition including
untreated proppant, treated proppant, crosslink treated proppant,
or mixtures and combinations thereof. In other embodiments, the
treated proppant comprises a proppant having a partial or complete
coating of an aggregating composition comprising an amine-phosphate
reaction product, amine component, amine polymeric aggregating
composition, a coacervate aggregating composition, or mixtures and
combinations thereof. In other embodiments, the crosslink treated
proppant comprises a proppant having a partial or complete coating
of an aggregating composition comprising an amine-phosphate
reaction product, amine component, a coacervate aggregating
composition, or mixtures and combinations thereof crosslinked with
a coating crosslinking composition comprising inorganic
crosslinking agents, organic crosslinking agents, or mixtures and
combinations thereof. In other embodiments, the proppant
compositions differ in at least one of the following properties:
(a) an amounts of untreated and treated proppant, (b) densities of
the untreated and/or treated proppants, (c) sizes of the untreated
and/or treated proppants, (d) shapes of the untreated and/or
treated proppants, or (e) strengths of the untreated and/or treated
proppants. In other embodiments, the proppant compositions further
include (i) a non-erodible fiber, (ii) an erodible material
comprising erodible particles, erodible fibers, or mixtures and
combinations thereof, or (iii) mixtures or combinations thereof. In
other embodiments, the proppant settling rate is control by
adjusting a pumping rates. In other embodiments, the viscosified
fracturing fluids differ in the viscosifying composition. In other
embodiments, the injecting step comprises injecting the at least
two different fracturing fluids according to an injection sequence.
at least one of the fluids is proppant-free and at least one of the
fluids includes a proppant composition. In other embodiments, the
injection sequence comprises injecting the at least two different
fracturing fluids in alternating stages during the fracturing
operation. In other embodiments, the methods further comprises
prior to the proppant placement step, a pad stage comprising
injecting into the a pad fluid comprising a base fluid and a
viscosifying composition or a base fluid, a viscosifying
composition, and an aggregating composition.
[0150] Embodiments of this invention relate to methods for
fracturing a subterranean formation comprising a proppant placement
stage comprising injecting into the formation penetrated by a
wellbore at least two different fracturing fluid according to an
injection sequence, where the fracturing fluids differ in at least
one property. In certain embodiments, the methods further comprises
prior to the proppant placement step, a pad stage comprising
injecting into the a pad fluid comprising a base fluid and a
viscosifying composition or a base fluid, a viscosifying
composition, and an aggregating composition. In certain
embodiments, the properties include a fluid composition, a fluid
pressure, a fluid temperature, a fluid pulse duration, a proppant
settling rate, proppant types, proppant sizes, proppant strengths,
proppant shapes, or mixtures and combinations thereof. In certain
embodiments, the fracturing fluids are selected from the group
consisting of (a) proppant-free fluids including (i) a base fluid
or (ii) a base fluid and an aggregating composition and/or a
coating crossslinking composition and/or a viscosifying composition
and (b) proppant-containing fluids including (i) a base fluid, a
viscosifying composition, and a proppant composition or (ii) a base
fluid, a viscosifying composition, a proppant composition and an
aggregating composition and/or a coating crossslinking composition.
In other embodiments, the aggregating composition comprising an
amine-phosphate reaction product, amine component, amine polymeric
aggregating composition, a coacervate aggregating composition, or
mixtures and combinations thereof. In other embodiments, the
proppant composition including untreated proppant, treated
proppant, or mixtures and combinations thereof. In other
embodiments, the coating crosslinking composition comprising
inorganic crosslinking agents, organic crosslinking agents, or
mixtures and combinations thereof. In other embodiments, the
treated proppant comprises a proppant having a partial or complete
coating of an aggregating composition comprising an amine-phosphate
reaction product, amine component, amine polymeric aggregating
composition, a coacervate aggregating composition, or mixtures and
combinations thereof. In other embodiments, the crosslink treated
proppant comprises a proppant having a partial or complete coating
of an aggregating composition comprising an amine-phosphate
reaction product, amine component, a coacervate aggregating
composition, or mixtures and combinations thereof crosslinked with
a coating crosslinking composition comprising inorganic
crosslinking agents, organic crosslinking agents, or mixtures and
combinations thereof. In other embodiments, the proppant
compositions differ in at least one of the following properties:
(a) an amounts of untreated and treated proppant, (b) densities of
the untreated and/or treated proppants, (c) sizes of the untreated
and/or treated proppants, (d) shapes of the untreated and/or
treated proppants, or (e) strengths of the untreated and/or treated
proppants. In other embodiments, the proppant compositions further
include (i) a non-erodible fiber, (ii) an erodible material
comprising erodible particles, erodible fibers, or mixtures and
combinations thereof, or (iii) mixtures or combinations thereof. In
other embodiments, the proppant settling rate is control by
adjusting a pumping rates. In other embodiments, the viscosified
fracturing fluids differ in the viscosifying composition. In other
embodiments, the injecting step comprises injecting the at least
two different fracturing fluids according to an injection sequence.
In other embodiments, at least one of the fluids is proppant-free
and at least one of the fluids includes a proppant composition. In
other embodiments, the injection sequence comprises injecting the
at least two different fracturing fluids in alternating stages
during the fracturing operation. In other embodiments, the methods
further comprising after the proppant placement step, a tail-in
stage comprising injecting into the a tail-in fluid comprising (i)
a base fluid, a viscosifying composition, and a proppant
composition or (ii) a base fluid, a viscosifying composition, a
proppant composition, and an aggregating composition.
[0151] Embodiments of this invention relate to methods for placing
a proppant/flow path network in fractures in a fracturing layer
penetrated by a wellbore, the method comprises a proppant placement
stage comprising injecting, into the fracturing layer above
fracturing pressure through a pattern of perforations comprising
groups of perforations separated by non-perforated spans, a
sequence of slugs of at least one proppant-free fluid selected from
the group consisting of a non-viscosified proppant-free fluid or a
viscosified proppant-free fluid and at least one
proppant-containing fluid selected from the group consisting of a
non-viscosified proppant-containing fluid or a viscosified
proppant-containing fluid. In certain embodiments, the
non-viscosified proppant-free fluid comprises (a) a base fluid or
(b) a base fluid and an aggregating composition and/or a coating
crosslinking composition. In other embodiments, the viscosified
proppant-free fluid comprises (a) a base fluid and a viscosifying
composition or (b) a base fluid, a viscosifying composition, and an
aggregating composition and/or a coating crosslinking composition.
In other embodiments, the non-viscosified proppant-containing
comprises (a) a base fluid and a proppant composition, or (b) a
base fluid, a proppant composition, and an aggregating composition
and/or a coating crosslinking composition. In other embodiments,
the viscosified proppant-containing comprises (a) a base fluid, a
viscosifying composition and, a proppant composition or (b) a base
fluid, a viscosifying composition, a proppant composition, and an
aggregating composition and/or a coating crosslinking composition.
In other embodiments, the aggregating composition comprises an
amine-phosphate reaction product, amine component, amine polymeric
aggregating composition, a coacervate aggregating composition, or
mixtures and combinations thereof. In other embodiments, the
coating crosslinking composition comprising inorganic crosslinking
agents, organic crosslinking agents, or mixtures and combinations
thereof. In other embodiments, the proppant-containing fluids form
proppant pillars within the fractures during fracturing and/or
after fracturing as the fractures closes. In other embodiments, the
methods further comprises causing the sequence of slugs injected
through neighboring perforation groups to move through the
fractures at different rates. In other embodiments, at least one of
the parameters slug volume, slug composition, proppant composition,
proppant sizes, proppant shapes, proppant densities, proppant
strengths, proppant concentrations, pattern length, number of
perforation groups, perforation group separations, perforation
group orientations, number of holes in each perforation group,
perforation group shot densities, perforation group lengths, number
of non-perforation spans, non-perforation span lengths, methods of
perforation, or combinations thereof change according to the slug
sequence. In other embodiments, the proppant composition comprises
a first amount of an untreated proppant, a second amount of a
treated proppant, a third amount of a crosslink treated proppant, a
fourth amount of an erodible or dissolvable proppant, and a fifth
amount of a non-erodible fiber. In other embodiments, the treated
proppant comprises a proppant having a partial or complete coating
of the aggregating composition. In other embodiments, the crosslink
treated proppant comprises a proppant having a partial or complete
coating of an aggregating composition comprising an amine-phosphate
reaction product, amine component, a coacervate aggregating
composition, or mixtures and combinations thereof crosslinked with
a coating crosslinking composition comprising inorganic
crosslinking agents, organic crosslinking agents, or mixtures and
combinations thereof. In other embodiments, the erodible or
dissolvable proppant comprises erodible or dissolvable organic
particles, erodible or dissolvable organic fibers, erodible or
dissolvable inorganic particles, and/or erodible or dissolvable
inorganic fibers. In other embodiments, the non-erodible fibers
comprise non-erodible organic fibers and/or non-erodible inorganic
fibers. In other embodiments, a sum of the second and third amounts
is 100 wt. %, the first, fourth and fifth amounts may range between
0 wt. % and 100 wt. %, and the amounts may sum to values greater
than 100%. In other embodiments, the methods further comprises
prior to the proppant placement step, a pad stage comprising
continuously injecting a viscosified proppant-free fluid into the
fracturing fluid under fracturing conditions to form or elongate
fractures. In other embodiments, the methods further comprises
after the proppant placement step, a tail-in-stage comprising
continuously injecting a viscosified proppant-containing fluid into
the fracturing fluid.
[0152] Embodiments of this invention relate to methods for
heterogeneous proppant placement in a fracture in a fracturing
layer, the method comprising a) a proppant placement stage
comprising injecting, into the fracturing layer above fracturing
pressure through a pattern of perforations comprising groups of
perforations separated by non-perforated spans, a sequence of slugs
of at least one proppant-free fluid selected from the group
consisting of a non-viscosified proppant-free fluid or a
viscosified proppant-free fluid and at least one
proppant-containing fluid selected from the group consisting of a
non-viscosified proppant-containing fluid or a viscosified
proppant-containing fluid, and b) causing the sequence of slugs
injected through neighboring perforation groups to move through the
fractures at different rates. In certain embodiments, the
non-viscosified proppant-free fluid comprises (a) a base fluid or
(b) a base fluid and an aggregating composition and/or a coating
crosslinking composition. In other embodiments, the viscosified
proppant-free fluid comprises (a) a base fluid and a viscosifying
composition or (b) a base fluid, a viscosifying composition, and an
aggregating composition and/or a coating crosslinking composition.
In other embodiments, the non-viscosified proppant-containing
comprises (a) a base fluid and a proppant composition, or (b) a
base fluid, a proppant composition, and an aggregating composition
and/or a coating crosslinking composition. In other embodiments,
the viscosified proppant-containing comprises (a) a base fluid, a
viscosifying composition and, a proppant composition or (b) a base
fluid, a viscosifying composition, a proppant composition, and an
aggregating composition and/or a coating crosslinking composition.
In other embodiments, the aggregating composition comprises an
amine-phosphate reaction product, amine component, amine polymeric
aggregating composition, a coacervate aggregating composition, or
mixtures and combinations thereof. In other embodiments, the
coating crosslinking composition comprising inorganic crosslinking
agents, organic crosslinking agents, or mixtures and combinations
thereof. In other embodiments, the proppant-containing fluids form
proppant pillars within the fractures during fracturing and/or
after fracturing as the fractures closes. In other embodiments, the
methods further comprises prior to the proppant placement step, a
pad stage comprising continuously injecting a viscosified
proppant-free fluid into the fracturing fluid under fracturing
conditions to form or elongate fractures. In other embodiments, the
methods further comprises after the proppant placement step, a
tail-in-stage comprising continuously injecting a viscosified
proppant-containing fluid into the fracturing fluid. In other
embodiments, at least one of the parameters slug volume, slug
composition, proppant composition, proppant sizes, proppant shapes,
proppant densities, proppant strengths, proppant concentrations,
pattern length, number of perforation groups, perforation group
separation, perforation group orientations, number of holes in each
perforation group, perforation group shot densities, perforation
group lengths, number of non-perforation spans, non-perforation
span lengths, methods of perforation, or combinations thereof
change according to the slug sequence. In other embodiments, a
volume of the proppant-containing fluids is less than a volume of
the proppant-free fluids. In other embodiments, a number of holes
in each of the perforation groups is the same or different. In
other embodiments, an orientations of all of the perforation groups
are the same or different. In other embodiments, a diameter of
holes in all of the perforation groups is the same or different. In
other embodiments, perforation group lengths of all the perforation
groups are the same or different. In other embodiments, at least
two different perforation methods for forming the perforation
groups are used. In other embodiments, some of the groups are
produced using an underbalanced perforation technique and some of
the groups are produced using an overbalanced perforation
technique. In other embodiments, at least two perforation groups
allow flow of a sequence of slugs of the proppant-free fluid and
the proppant-containing fluid are separated by a perforation group
having sufficiently small perforations that the proppant bridges
and proppant-free fluids enter the formation therethrough. In other
embodiments, every pair of perforation groups that produce a
sequence of slugs of the proppant-free fluids and the
proppant-containing fluids are separated by a perforation group
having sufficiently small perforations that the proppant bridges
and proppant-free fluid enters the formation therethrough. In other
embodiments, a number of perforation groups is between 2 and 300.
In other embodiments, the number of groups of perforations is
between 2 and 100. In other embodiments, the perforation group
length is between 0.15 m and 3.0 m. In other embodiments, the
perforation group separation is from 0.30 m to 30 m. In other
embodiments, the perforation shot density is from 1 to 30 shots per
0.3 m. In other embodiments, a fluid injection design is determined
from a mathematical model. In other embodiments, a perforation
pattern design is determined from a mathematical model. In other
embodiments, the proppant pillars are a proppant/flow pathway
network in the fractures such that the pillars do not extend over
an entire dimension of the fractures parallel to the wellbore but
are interrupted by flow paths that lead to the wellbore. In other
embodiments, the proppant slugs have a volume between 80 and 16,000
liters. In other embodiments, the perforations are slots cut into
tubing lining the wellbore.
[0153] Embodiments of this invention relate to compositions
comprising a subterranean formation penetrated by a wellbore, where
the formation includes fractures having a proppant/flow pathway
network, where the network comprises a plurality ofproppant
clusters forming pillars and a plurality of flow pathways extending
through the network to the wellbore improving fluid flow into or
out of the fractures. In certain embodiments, the proppant clusters
comprises a first amount of untreated proppant, a second amount of
treated proppant, a third amount of a crosslink treated proppant,
and a fourth amount of non-erodible fibers. In other embodiments,
the treated proppant comprises a proppant having a partial or
complete coating of an aggregating composition comprising an
amine-phosphate reaction product, amine component, amine polymeric
aggregating composition, a coacervate aggregating composition, or
mixtures and combinations thereof. In other embodiments, the
crosslink treated proppant comprises a proppant having a partial or
complete coating of an aggregating composition comprising an
amine-phosphate reaction product, amine component, a coacervate
aggregating composition, or mixtures and combinations thereof
crosslinked with a coating crosslinking composition comprising
inorganic crosslinking agents, organic crosslinking agents, or
mixtures and combinations thereof. In other embodiments, the second
and third amounts are sufficient: (a) to form the network in the
fractures, (b) to maintain the clusters substantially in tact, if
the clusters move or break up and reform within the fractures
during and/or after a fracturing operation, (c) to enable and
enhance fluid flow into and out of the formation through the
fractures, (d) to capture formation fines during and/or after a
fracturing operation, or during a injection operation, or during
production operation, or (e) mixtures and combinations thereof. In
other embodiments, the network comprises proppant-rich regions and
proppant-lean regions, where the proppant-lean regions include no
or less than 10% of clusters in the proppant-rich regions. In other
embodiments, the untreated proppant is selected from the group
consisting of sand, nut hulls, ceramics, bauxites, glass, natural
materials, plastic beads, particulate metals, drill cuttings, and
combinations thereof. In other embodiments, the treated proppant
comprising the untreated proppant including a partial or complete
coating of the aggregating composition. In other embodiments, the
second amount is 100 wt. %, the first and third amounts may range
between 0 wt. % and 100 wt. %, and the amounts may sum to values
greater than 100%. In other embodiments, the proppant clusters
further comprise a fifth amount of erodible or dissolvable proppant
particles and/or fibers, the erodible or dissolvable proppant
particles and/or fibers that form a plurality of erodible or
dissolvable clusters within the network, which erode or dissolve to
from additional flow pathways in network. In other embodiments, a
sum of the second and third amounts is 100 wt. %, the first, fourth
and fifth amounts may range between 0 wt. % and 100 wt. %, and the
amounts may sum to values greater than 100%.
[0154] Embodiments of this invention relate to compositions
comprising a subterranean formation penetrated by a wellbore, where
the formation includes fractures having a proppant/flow pathway
network, where the network comprises a plurality of proppant
clusters forming pillars, a plurality of erodible or dissolvable
clusters, and a plurality of flow pathways extending through the
network to the wellbore improving fluid flow into or out of the
fractures. In certain embodiments, the proppant clusters comprises
proppant composition including a first amount of untreated
proppant, a second amount of treated proppant, a third amount of
crosslink treated proppant, a fourth amount of erodible or
dissolvable proppant particles and/or fibers, and a fifth amount
ofnon-erodible fibers. In other embodiments, the treated proppant
comprises a proppant having a partial or complete coating of an
aggregating composition comprising an amine-phosphate reaction
product, amine component and amine-phosphate reaction product,
amine polymeric aggregating composition, a coacervate aggregating
composition, or mixtures and combinations thereof. In other
embodiments, the crosslink treated proppant comprises a proppant
having a partial or complete coating of an aggregating composition
comprising an amine-phosphate reaction product, amine component, a
coacervate aggregating composition, or mixtures and combinations
thereof crosslinked with a coating crosslinking composition
comprising inorganic crosslinking agents, organic crosslinking
agents, or mixtures and combinations thereof. In other embodiments,
the second and thirds amounts are sufficient: (a) to form the
clusters in the fracture, (b) to maintain the clusters
substantially in tact, if the mobile proppant island moves within a
formation during fracturing operations, (c) to enable and enhance
fluid flow from the formation through the fracture toward the
wellbore, (d) to capture formation fines during fracturing
operations, injection operations, or production operations, or (e)
mixtures and combinations thereof. In other embodiments, the
network comprises proppant-rich regions and proppant-lean regions,
where the proppant-lean regions include no or less than 10% of
clusters in the proppant-rich regions. In other embodiments, the
untreated proppant is selected from the group consisting of sand,
nut hulls, ceramics, bauxites, glass, natural materials, plastic
beads, particulate metals, drill cuttings, and combinations
thereof. In other embodiments, the treated proppant comprise the
untreated proppant including a partial or complete coating of the
aggregating composition. In other embodiments, a sum of the second
and third amounts is 100 wt. %, the first, fourth and fifth amounts
may range between 0 wt. % and 100 wt. %, and the amounts may sum to
values greater than 100%.
[0155] Compositional Ranges Useful in the Invention
[0156] Fracturing fluids are all based on 100 wt. % of a base fluid
and various wt. % of the other components so that the final
fracturing fluid weight percentages may sum to greater than 100%,
thus, the other components represent relative amounts. These
formulations are therefore similar to rubber compositions which are
expressed relative amounts based on 100 parts rubber. With this in
mind, the fracturing fluids may include 100 wt. % of a base fluid
and varying amounts of: an aggregating composition, an aggregating
coating crosslinking composition, a viscosifying composition, a
proppant composition, and other additives. Table 1 tabulations
permitted proppant-free fracturing fluid compositions in ranges of
components.
TABLE-US-00001 TABLE 1 Proppant-Free Fluids - All Amount in Weight
Percentages Type BF.sup.a AC.sup.b ACC.sup.c VC.sup.d OC.sup.e
PC.sup.f 1 100 0 0 0 0 0 2 100 0.01-20 0 0 0 0 (0.01-10) {0.01-5} 3
100 0 0.01-20 0 0 0 (0.01-10) {0.01-5} 4 100 0 0 0.01-20 0 0
(0.01-10) {0.01-5} 5 100 0 0 0 0.01-20 0 (0.01-10) {0.01-5} 6 100
0.01-20 0.01-20 0 0 0 (0.01-10) (0.01-10) {0.01-5} {0.01-5} 7 100
0.01-20 0 0.01-20 0 0 (0.01-10) (0.01-10) {0.01-5} {0.01-5} 8 100
0.01-20 0 0 0.01-20 0 (0.01-10) (0.01-10) {0.01-5} {0.01-5} 9 100 0
0.01-20 0.01-20 0 0 (0.01-10) (0.01-10) {0.01-5} {0.01-5} 10 100 0
0.01-20 0 0.01-20 0 (0.01-10) (0.01-10) {0.01-5} {0.01-5} 11 100 0
0 0.01-20 0.01-20 0 (0.01-10) (0.01-10) {0.01-5} {0.01-5} 12 100
0.01-20 0.01-20 0.01-20 0 0 (0.01-10) (0.01-10) (0.01-10) {0.01-5}
{0.01-5} {0.01-5} 13 100 0.01-20 0.01-20 0 0.01-20 0 (0.01-10)
(0.01-10) (0.01-10) {0.01-5} {0.01-5} {0.01-5} 14 100 0.01-20 0
0.01-20 0.01-20 0 (0.01-10) (0.01-10) (0.01-10) {0.01-5} {0.01-5}
{0.01-5} 15 100 0 0.01-20 0.01-20 0.01-20 0 (0.01-10) (0.01-10)
(0.01-10) {0.01-5} {0.01-5} {0.01-5} 16 100 0.01-20 0.01-20 0.01-20
0.01-20 0 (0.01-10) (0.01-10) (0.01-10) (0.01-10) {0.01-5} {0.01-5}
{0.01-5} {0.01-5} .sup.abase fluid, .sup.baggregating composition,
.sup.ccoating crosslinking composition, .sup.dviscosifying
composition, .sup.eother additives, and .sup.fproppant composition
- ( ) narrower range, { } still narrower range, (( )) still
narrower range
[0157] Table 2 tabulates permitted proppant-containing fracturing
fluids in ranges of components.
TABLE-US-00002 TABLE 2 Proppant Containing Fluids - All Amount in
Weight Percentages Type BF.sup.a AC.sup.b ACC.sup.c VC.sup.d
OC.sup.e PC.sup.f 1 100 0 0 0 0 0.1-400 (0.1-300) {0.1-200}
((.01-100)) 2 100 0.01-20 0 0 0 0.1-400 (0.01-10) (0.1-300)
{0.01-5} {0.1-200} ((.01-100)) 3 100 0 0.01-20 0 0 0.1-400
(0.01-10) (0.1-300) {0.01-5} {0.1-200} ((.01-100)) 4 100 0 0
0.01-20 0 0.1-400 (0.01-10) (0.1-300) {0.01-5} {0.1-200}
((.01-100)) 5 100 0 0 0 0.01-20 0.1-400 (0.01-10) (0.1-300)
{0.01-5} {0.1-200} ((.01-100)) 6 100 0.01-20 0.01-20 0 0 0.1-400
(0.01-10) (0.01-10) (0.1-300) {0.01-5} {0.01-5} {0.1-200}
((.01-100)) 7 100 0.01-20 0 0.01-20 0 0.1-400 (0.01-10) (0.01-10)
(0.1-300) {0.01-5} {0.01-5} {0.1-200} ((.01-100)) 8 100 0.01-20 0 0
0.01-20 0.1-400 (0.01-10) (0.01-10) (0.1-300) {0.01-5} {0.01-5}
{0.1-200} ((.01-100)) 9 100 0 0.01-20 0.01-20 0 0.1-400 (0.01-10)
(0.01-10) (0.1-300) {0.01-5} {0.01-5} {0.1-200} ((.01-100)) 10 100
0 0.01-20 0 0.01-20 0.1-400 (0.01-10) (0.01-10) (0.1-300) {0.01-5}
{0.01-5} {0.1-200} ((.01-100)) 11 100 0 0 0.01-20 0.1-20 0.1-400
(0.01-10) (0.1-10) (0.1-300) {0.01-5} {0.01-5} {0.1-200}
((.01-100)) 12 100 0.01-20 0.01-20 0.01-20 0 0.1-400 (0.01-10)
(0.01-10) (0.01-10) (0.1-300) {0.01-5} {0.01-5} {0.01-5} {0.1-200}
((.01-100)) 13 100 0.01-20 0.01-20 0 0.01-20 0.1-400 (0.01-10)
(0.01-10) (0.01-10) (0.1-300) {0.01-5} {0.01-5} {0.01-5} {0.1-200}
((.01-100)) 14 100 0.01-20 0 0.01-20 0.01-20 0.1-400 (0.01-10)
(0.01-10) (0.01-10) (0.1-300) {0.01-5} {0.01-5} {0.01-5} {0.1-200}
((.01-100)) 15 100 0 0.01-20 0.01-20 0.01-20 0.1-400 (0.01-10)
(0.01-10) (0.01-10) (0.1-300) {0.01-5} {0.01-5} {0.01-5} {0.1-200}
((.01-100)) 16 100 0.01-20 0.01-20 0.01-20 0.01-20 0.1-400
(0.01-10) (0.01-10) (0.01-10) (0.01-10) (0.1-300) {0.01-5} {0.01-5}
{0.01-5} {0.01-5} {0.1-200} ((.01-100)) .sup.abase fluid,
.sup.baggregating composition, .sup.ccoating crosslinking
composition, .sup.dviscosifying composition, .sup.eother additives,
and .sup.fproppant composition - ( ) narrower range, { } still
narrower range, (( )) still narrower range
[0158] In certain embodiments, the viscosifying compositions
include from about 80 wt. % to about 99 wt. % of one viscosifying
agent or a plurality of viscosifying agents and from about 20 wt. %
to about 0.1 wt. % of one crosslinking agent or a plurality of
crosslinking agents. A list of viscosifying agents and crosslinking
agents are set forth in the Suitable Reagents section herein.
[0159] In certain embodiments, the aggregating composition may
comprise a single aggregating agent or a plurality of aggregating
agents in any relative mixture, where the agent and/or mixture
selection may be tailored to formation and proppant properties and
characteristics.
[0160] In certain embodiments, the proppant composition of each
proppant-containing fracturing fluid may include from 0 wt. % to
100 wt. % of one untreated proppant or a plurality of untreated
proppants and from 0 wt. % to 100 wt. % of one treated proppant or
a plurality of treated proppants, where the treated proppants
comprise untreated proppants treated with one aggregating agent or
untreated proppants treated with a plurality of the aggregating
agents to form partial or complete aggregating coating on the
proppants altering their aggregating propensity from low to maximal
aggregating propensity according to the information shown in FIG.
6. It should be recognized that by changing the amount of
aggregating composition used or the extend of the aggregating
coating on treated proppants, the relative or bulk aggregating
propensity per the table of FIG. 6 may be altered to any desired
aggregating propensity to permit different proppant pillar or
island formation within fractures formed in a formation during
formation fracturing.
[0161] Suitable Reagents Used in the Invention
Base Fluids
[0162] The base fluids for use in this invention include, without
limitation, any liquid base fluid suitable for use in oil and gas
producing wells or injections wells, or mixtures and combinations
thereof. Exemplary liquid base fluids include, without limitation,
aqueous base fluids, organic base fluids, water-in-oil base fluids,
oil-in-water base fluids, any other base fluids used in fracturing
fluids, viscosified versions thereof, or mixtures and combinations
thereof. Exemplary aqueous base fluids include water, tap water,
production water, salt water, brines, or mixtures and combinations
thereof. Exemplary brines include, without limitation, sodium
chloride brines, potassium chloride brines, calcium chloride
brines, magnesium chloride brines, tetramethyl ammonium chloride
brines, other chloride brines, phosphate brines, nitrate brines,
other salt brines, or mixtures and combinations thereof.
[0163] Aqueous Base Fluids
[0164] Aqueous base fluids will generally comprise water, consist
essentially of water, or consist of water. Water will typically be
a major component by weight (.gtoreq.50 wt. % of the aqueous base
fluids. The water may be potable or non-potable. The water may be
brackish or contain other materials typical of sources of water
found in or near oil fields. For example, it is possible to use
fresh water, brine, or even water to which any salt, such as an
alkali metal or alkali earth metal salt (NaCO.sub.3, NaCl, KCl,
etc.) has been added. The aqueous fracturing fluids generally
include at least about 80 wt. % of an aqueous base fluid. In other
embodiments, the aqueous fracturing fluids including 80 wt. %, 85
wt. %, 90 wt. %, and 95 wt. % of an aqueous base fluid.
[0165] Organic Base Fluids
[0166] Organic base fluids comprise of a liquid organic carrier,
consist essentially of a liquid organic carrier, or consist of a
liquid organic carrier or a hydrcarbon base fluid or a hydrocarbon
base fluid include a hydrocarbon soluble polymer. The organic
fracturing fluids generally include at least about 80 wt. % of an
organic base fluid. In other embodiments, the aqueous fracturing
fluids including 80 wt. %, 85 wt. %, 90 wt. %, and 95 wt. % of an
organic base fluid.
[0167] Hydrocarbon Base Fluids
[0168] Suitable hydrocarbon base fluids for use in this invention
includes, without limitation, synthetic hydrocarbon fluids,
petroleum based hydrocarbon fluids, natural hydrocarbon
(non-aqueous) fluids or other similar hydrocarbons or mixtures or
combinations thereof. The hydrocarbon fluids for use in the present
invention have viscosities ranging from about 5.times.10.sup.-6 to
about 600.times.10.sup.-6 m.sup.2/s (5 to about 600 centistokes).
Exemplary examples of such hydrocarbon fluids include, without
limitation, polyalphaolefins, polybutenes, polyesters, biodiesels,
simple low molecular weight fatty esters of vegetable or vegetable
oil fractions, simple esters of alcohols such as Exxate from Exxon
Chemicals, vegetable oils, animal oils or esters, other essential
oil, diesel, diesel having a low or high sulfur content, kerosene,
jet-fuel, white oils, mineral oils, mineral seal oils, hydrogenated
oil such as PetroCanada HT-40N or IA-35 or similar oils produced by
Shell Oil Company, internal olefins (IO) having between about 12
and 20 carbon atoms, linear alpha olefins having between about 14
and 20 carbon atoms, polyalpha olefins having between about 12 and
about 20 carbon atoms, isomerized alpha olefins (IAO) having
between about 12 and about 20 carbon atoms, VM&P Naptha,
Linpar, Parafins having between 13 and about 16 carbon atoms, and
mixtures or combinations thereof.
[0169] Suitable polyalphaolefins (PAOs) include, without
limitation, polyethylenes, polypropylenes, polybutenes,
polypentenes, polyhexenes, polyheptenes, higher PAOs, copolymers
thereof, and mixtures thereof. Exemplary examples of PAOs include
PAOs sold by Mobil Chemical Company as SHF fluids and PAOs sold
formerly by Ethyl Corporation under the name ETHYLFLO and currently
by Albemarle Corporation under the trade name Durasyn. Such fluids
include those specified as ETYHLFLO 162, 164, 166, 168, 170, 174,
and 180. Well suited PAOs for use in this invention include bends
of about 56% of ETHYLFLO now Durasyn 174 and about 44% of ETHYLFLO
now Durasyn 168.
[0170] Exemplary examples of polybutenes include, without
limitation, those sold by Amoco Chemical Company and Exxon Chemical
Company under the trade names INDOPOL and PARAPOL, respectively.
Well suited polybutenes for use in this invention include Amoco's
INDOPOL 100.
[0171] Exemplary examples of polyester include, without limitation,
neopentyl glycols, trimethylolpropanes, pentaerythriols,
dipentaerythritols, and diesters such as dioctylsebacate (DOS),
diactylazelate (DOZ), and dioctyladipate.
[0172] Exemplary examples of petroleum based fluids include,
without limitation, white mineral oils, paraffinic oils, and
medium-viscosity-index (MVI) naphthenic oils having viscosities
ranging from about 5.times.10.sup.-6 to about 600.times.10.sup.-6
m.sup.2/s (5 to about 600 centistokes) at 40.degree. C. Exemplary
examples of white mineral oils include those sold by Witco
Corporation, Arco Chemical Company, PSI, and Penreco. Exemplary
examples of paraffinic oils include solvent neutral oils available
from Exxon Chemical Company, high-viscosity-index (HVI) neutral
oils available from Shell Chemical Company, and solvent treated
neutral oils available from Arco Chemical Company. Exemplary
examples of MVI naphthenic oils include solvent extracted coastal
pale oils available from Exxon Chemical Company, MVI extracted/acid
treated oils available from Shell Chemical Company. Chemical
Company, and naphthenic oils sold under the names HydroCal and
Calsol by Calumet and hydrogenated oils such as HT-40N and IA-35
from PetroCanada or Shell Oil Company or other similar hydrogenated
oils.
[0173] Exemplary examples of vegetable oils include, without
limitation, castor oils, corn oil, olive oil, sunflower oil, sesame
oil, peanut oil, palm oil, palm kernel oil, coconut oil, butter
fat, canola oil, rape seed oil, flax seed oil, cottonseed oil,
linseed oil, other vegetable oils, modified vegetable oils such as
crosslinked castor oils and the like, and mixtures thereof.
Exemplary examples of animal oils include, without limitation,
tallow, mink oil, lard, other animal oils, and mixtures thereof.
Other essential oils will work as well. Of course, mixtures of all
the above identified oils can be used as well.
[0174] Hydrocarbon Soluble Polymers
[0175] Suitable polymers for use as anti-settling additives or
polymeric suspension agents in this invention include, without
limitation, linear polymers, block polymers, graft polymers, star
polymers or other multi-armed polymers, which include one or more
olefin monomers and/or one or more diene monomers and mixtures or
combinations thereof. The term polymer as used herein refers to
homo-polymers, co-polymers, polymers including three of more
monomers (olefin monomers and/or diene monomers), polymer including
oligomeric or polymeric grafts, which can comprise the same or
different monomer composition, arms extending form a polymeric
center or starring reagent such as tri and tetra valent linking
agents or divinylbenzene nodes or the like, and homo-polymers
having differing tacticities or microstructures. Exemplary examples
are styrene-isoprene copolymers (random or block), triblocked,
multi-blocked, styrene-butadiene copolymer (random or block),
ethylene-propylene copolymer (random or block), sulphonated
polystyrene polymers, alkyl methacrylate polymers, vinyl
pyrrolidone polymers, vinyl pyridine, vinyl acetate, or mixtures or
combinations thereof.
[0176] Suitable olefin monomer include, without limitation, any
monounsaturated compound capable of being polymerized into a
polymer or mixtures or combinations thereof. Exemplary examples
include ethylene, propylene, butylene, and other alpha olefins
having between about 5 and about 20 carbon atoms and sufficient
hydrogens to satisfy the valency requirement, where one or more
carbon atoms can be replaced by B, N, O, P, S, Ge or the like and
one or more of the hydrogen atoms can be replaced by F, Cl, Br, I,
OR, SR, COOR, CHO, C(O)R, C(O)NH2, C(O)NHR, C(O)NRR', or other
similar monovalent groups, polymerizable internal mono-olefinic
monomers or mixtures or combinations thereof, where R and R' are
the same or different and are carbyl group having between about 1
to about 16 carbon atoms and where one or more of the carbon atoms
and hydrogen atoms can be replaced as set forth immediately
above.
[0177] Suitable diene monomer include, without limitation, any
doubly unsaturated compound capable of being polymerized into a
polymer or mixtures or combinations thereof. Exemplary examples
include 1,3-butadiene, isoprene, 2,3-dimethyl butadiene, or other
polymerizable diene monomers.
[0178] The inventors have found that Infineum SV150, an
isoprene-styrene di-block and starred polymer, offers superior
permanent shear stability and thickening efficiency due to its
micelle forming nature.
[0179] Suitable hydrocarbon base fuels include, without limitation,
t and mineral oil or diesel oil before adding organophillic clays,
polar activator, the additive to be suspended (Guar or Deriatized
Guar, e.g. CMHPG) and the dispersing surfactant in concentrations
between 0.10-5.0% w/w.
[0180] Viscoelastic Base Fluids
[0181] Viscoelastic base fluids comprise a liquid carrier including
viscoelastic surfactant (VES) or a VES gel.
[0182] The surfactant can generally be any surfactant. The
surfactant is preferably viscoelastic. The surfactant is preferably
anionic. The anionic surfactant can be an alkyl sarcosinate. The
alkyl sarcosinate can generally have any number of carbon atoms.
Presently preferred alkyl sarcosinates have about 12 to about 24
carbon atoms. The alkyl sarcosinate can have about 14 to about 18
carbon atoms. Specific examples of the number of carbon atoms
include 12, 14, 16, 18, 20, 22, and 24 carbon atoms.
[0183] The anionic surfactant can have the chemical formula R.sub.1
CON(R.sub.2)CH.sub.2X, wherein R.sub.1 is a hydrophobic chain
having about 12 to about 24 carbon atoms, R.sub.2 is hydrogen,
methyl, ethyl, propyl, or butyl, and X is carboxyl or sulfonyl. The
hydrophobic chain can be an alkyl group, an alkenyl group, an
alkylarylalkyl group, or an alkoxyalkyl group. Specific examples of
the hydrophobic chain include a tetradecyl group, a hexadecyl
group, an octadecentyl group, an octadecyl group, and a docosenoic
group.
[0184] The surfactant can generally be present in any weight
percent concentration. Presently preferred concentrations of
surfactant are about 0.1% to about 15% by weight. A presently more
preferred concentration is about 0.5% to about 6% by weight.
Laboratory procedures can be employed to determine the optimum
concentrations for any particular situation.
[0185] The amphoteric polymer can generally be any amphoteric
polymer. The amphoteric polymer can be a nonionic water-soluble
homopolysaccharide or an anionic water-soluble polysaccharide. The
polymer can generally have any molecular weight, and is presently
preferred to have a molecular weight of at least about 500,000.
[0186] The polymer can be a hydrolyzed polyacrylamide polymer. The
polymer can be a scleroglucan, a modified scleroglucan, or a
scleroglucan modified by contact with glyoxal or glutaraldehyde.
The scleroglucans are nonionic water-soluble homopolysaccharides,
or water-soluble anionic polysaccharides, having molecular weights
in excess of about 500,000, the molecules of which consist of a
main straight chain formed of D-glucose units which are bonded by
.beta.-1,3-bonds and one in three of which is bonded to a side
D-glucose unit by means of a .beta.-1,6 bond. These polysaccharides
can be obtained by any of the known methods in the art, such as
fermentation of a medium based on sugar and inorganic salts under
the action of a microorganism of Sclerotium type A. A more complete
description of such scleroglucans and their preparations may be
found, for example, in U.S. Pat. Nos. 3,301,848 and 4,561,985,
incorporated herein by reference. In aqueous solutions, the
scleroglucan chains are combined in a triple helix, which explains
the rigidity of the biopolymer, and consequently its features of
high viscosity-increasing power and resistance to shearing
stress.
[0187] It is possible to use, as source of scleroglucan, the
scleroglucan which is isolated from a fermentation medium, the
product being in the form of a powder or of a more or less
concentrated solution in an aqueous and/or aqueous-alcoholic
solvent. Scleroglucans customarily used in applications in the
petroleum field are also preferred according to the present
invention, such as those which are white powders obtained by
alcoholic precipitation of a fermentation broth in order to remove
residues of the producing organism (mycelium, for example).
Additionally, it is possible to use the liquid reaction mixture
resulting from the fermentation and containing the scleroglucan in
solution. According to the present invention, further suitable
scleroglucans are the modified scleroglucan which result from the
treatment of scleroglucans with a dialdehyde reagent (glyoxal,
glutaraldehyde, and the like), as well as those described in U.S.
Pat. No. 6,162,449, incorporated herein by reference,
(b-1,3-scleroglucans with a cross-linked 3-dimensional structure
produced by Sclerotium rolfsii).
[0188] The polymer can be Aquatrol V (a synthetic compound which
reduces water production problems in well production; described in
U.S. Pat. No. 5,465,792, incorporated herein by reference), AquaCon
(a moderate molecular weight hydrophilic terpolymer based on
polyacrylamide capable of binding to formation surfaces to enhance
hydrocarbon production; described in U.S. Pat. No. 6,228,812,
incorporated herein by reference) and Aquatrol C (an amphoteric
polymeric material). Aquatrol V, Aquatrol C, and AquaCon are
commercially available from BJ Services Company.
[0189] The polymer can be a terpolymer synthesized from an anionic
monomer, a cationic monomer, and a neutral monomer. The monomers
used preferably have similar reactivities so that the resultant
amphoteric polymeric material has a random distribution of
monomers. The anionic monomer can generally be any anionic monomer.
Presently preferred anionic monomers include acrylic acid,
methacrylic acid, 2-acrylamide-2-methylpropane sulfonic acid, and
maleic anhydride. The cationic monomer can generally be any
cationic monomer. Presently preferred cationic monomers include
dimethyl-diallyl ammonium chloride, dimethylamino-ethyl
methacrylate, and allyltrimethyl ammonium chloride. The neutral
monomer can generally be any neutral monomer. Presently preferred
neutral monomers include butadiene, N-vinyl-2-pyrrolidone, methyl
vinyl ether, methyl acrylate, maleic anhydride, styrene, vinyl
acetate, acrylamide, methyl methacrylate, and acrylonitrile. The
polymer can be a terpolymer synthesized from acrylic acid (AA),
dimethyl diallyl ammonium chloride (DMDAC) or diallyl dimethyl
ammonium chloride (DADMAC), and acrylamide (AM). The ratio of
monomers in the terpolymer can generally be any ratio. A presently
preferred ratio is about 1:1:1.
[0190] Another presently preferred amphoteric polymeric material
(hereinafter "polymer 1") includes approximately 30% polymerized
AA, 40% polymerized AM, and 10% polymerized DMDAC or DADMAC with
approximately 20% free residual DMDAC or DADMAC which is not
polymerized due to lower relative reactivity of the DMDAC or DADMAC
monomer.
[0191] The fluid can further comprise one or more additives. The
fluid can further comprise a base. The fluid can further comprise a
salt. The fluid can further comprise a buffer. The fluid can
further comprise a relative permeability modifier. The fluid can
further comprise methylethylamine, monoethanolamine, triethylamine,
triethanolamine, sodium hydroxide, potassium hydroxide, potassium
carbonate, sodium chloride, potassium chloride, potassium fluoride,
KH.sub.2PO.sub.4, or K.sub.2HPO.sub.4. The fluid can further
comprise a proppant. Conventional proppants will be familiar to
those skilled in the art and include sand, resin coated sand
sintered bauxite and similar materials. The proppant can be
suspended in the fluid.
[0192] Sarcosine (N-methylglycine) is a naturally occurring amino
acid found in starfish, sea urchins and crustaceans. It can be
purchased from a variety of commercial sources, or alternately
produced by a number of synthetic routes known in the art including
thermal decomposition of caffeine in the presence of barium
hydroxide (Arch. Pharm. 232: 601, 1894); (Bull. Chem. Soc. Japan,
39: 2535, 1966); and numerous others (T. Shirai in Synthetic
Production and Utilization of Amino Acids; T. Kaneko, et al., Eds.;
Wiley, New York: pp. 184-186, 1974). Sodium sarcosinate is
manufactured commercially from formaldehyde, sodium cyanide and
methyl amine (U.S. Pat. Nos. 2,720,540 and 3,009,954). The
preferred sarcosinate are the condensation products of sodium
sarcosinate and a fatty acid chloride. The fatty acid chloride is
reacted with sodium sarcosinate under carefully controlled alkaline
conditions (i.e., the Schotten-Bauman reaction) to produce the
fatty sarcosinate sodium salt which is water soluble. Upon
acidification, the fatty sarcosine acid, which is also water
insoluble, is formed and may be isolated from the reaction medium.
The acyl sarcosines may be neutralized with bases such as the salts
of sodium, potassium, ammonia, or organic bases such as
triethanolamine in order to produce aqueous solutions.
[0193] Another surfactant useful in the fluids of this invention
are an anionic sarcosinate surfactant available commercially from
BJ Services Company as "M-Aquatrol" (MA). The MA-1 sarcosinate is a
viscous liquid surfactant with at least 94% oleoyl sarcosine. For
hydraulic fracturing, a sufficient quantity of the sarcosinate is
present in aqueous solution to provide sufficient viscosity to
suspend proppant during placement. The surfactant is preferably
present at about 0.5% to about 10% by weight, most preferably at
about 0.5% to about 6% by weight, based upon the weight of the
total fluid.
Viscosifying Agents
[0194] The hydratable polymer may be a water soluble
polysaccharide, such as galactomannan, cellulose, or derivatives
thereof.
[0195] Suitable hydratable polymers that may be used in embodiments
of the invention include any of the hydratable polysaccharides
which are capable of forming a gel in the presence of a
crosslinking agent. For instance, suitable hydratable
polysaccharides include, but are not limited to, galactomannan
gums, glucomannan gums, guars, derived guars, and cellulose
derivatives. Specific examples are guar gum, guar gum derivatives,
locust bean gum, Karaya gum, carboxymethyl cellulose, carboxymethyl
hydroxyethyl cellulose, and hydroxyethyl cellulose.
[0196] Presently preferred gelling agents include, but are not
limited to, guar gums, hydroxypropyl guar, carboxymethyl
hydroxypropyl guar, carboxymethyl guar, and carboxymethyl
hydroxyethyl cellulose. Suitable hydratable polymers may also
include synthetic polymers, such as polyvinyl alcohol,
polyacrylamides, poly-2-amino-2-methyl propane sulfonic acid, and
various other synthetic polymers and copolymers. Other suitable
polymers are known to those skilled in the art.
[0197] The hydratable polymer may be present in the fluid in
concentrations ranging from about 0.10% to about 5.0% by weight of
the aqueous fluid. In certain embodiments, the range for the
hydratable polymer is about 0.20% to about 0.80% by weight.
Viscosifying Agent Crosslinking Agents
[0198] The crosslinking agent may be a borate, titanate, or
zirconium-containing compound. For example, the crosslinking agent
can be sodium borate.times.H.sub.2O (varying waters of hydration),
boric acid, borate crosslinkers (a mixture of a titanate
constituent, preferably an organotitanate constituent, with a boron
constituent. The organotitanate constituent can be TYZOR.RTM.
titanium chelate esters from E.I du Pont de Nemours & Company.
The organotitanate constituent can be a mixture of a first
organotitanate compound having a lactate base and a second
organotitanate compound having triethanolamine base. The boron
constituent can be selected from the group consisting of boric
acid, sodium tetraborate, and mixtures thereof. These are described
in U.S. Pat. No. 4,514,309, incorporated herein by reference,
borate based ores such as ulexite and colemanite, Ti(IV)
acetylacetonate, Ti(IV) triethanolamine, Zr lactate, Zr
triethanolamine, Zr lactate-triethanolamine, or Zr
lactate-triethanolamine-triisopropanolamine. In some embodiments,
the well treatment fluid composition may further comprise a
proppant.
[0199] A suitable crosslinking agent can be any compound that
increases the viscosity of the fluid by chemical crosslinking,
physical crosslinking, or any other mechanisms. For example, the
gellation of a hydratable polymer can be achieved by crosslinking
the polymer with metal ions including boron, zirconium, and
titanium containing compounds, or mixtures thereof. One class of
suitable crosslinking agents is organotitanates. Another class of
suitable crosslinking agents is borates as described, for example,
in U.S. Pat. No. 4,514,309, incorporated herein by reference. The
selection of an appropriate crosslinking agent depends upon the
type of treatment to be performed and the hydratable polymer to be
used. The amount of the crosslinking agent used also depends upon
the well conditions and the type of treatment to be effected, but
is generally in the range of from about 10 ppm to about 1000 ppm of
metal ion of the crosslinking agent in the hydratable polymer
fluid. In some applications, the aqueous polymer solution is
crosslinked immediately upon addition of the crosslinking agent to
form a highly viscous gel. In other applications, the reaction of
the crosslinking agent can be retarded so that viscous gel
formation does not occur until the desired time.
[0200] In many instances, if not most, the viscosifying polymer is
crosslinked with a suitable crosslinking agent. The crosslinked
polymer has an even higher viscosity and is even more effective at
carrying proppant into the fractured formation. The borate ion has
been used extensively as a crosslinking agent, typically in high pH
fluids, for guar, guar derivatives and other galactomannans. See,
for example, U.S. Pat. No. 3,059,909, incorporated herein by
reference and numerous other patents that describe this classic
aqueous gel as a fracture fluid. Other crosslinking agents include,
for example, titanium crosslinkers (U.S. Pat. No. 3,888,312,
incorporated herein by reference), chromium, iron, aluminum, and
zirconium (U.S. Pat. No. 3,301,723, incorporated herein by
reference). Of these, the titanium and zirconium crosslinking
agents are typically preferred. Examples of commonly used zirconium
crosslinking agents include zirconium triethanolamine complexes,
zirconium acetylacetonate, zirconium lactate, zirconium carbonate,
and chelants of organic alphahydroxycorboxylic acid and zirconium.
Examples of commonly used titanium crosslinking agents include
titanium triethanolamine complexes, titanium acetylacetonate,
titanium lactate, and chelants of organic alphahydroxycorboxylic
acid and titanium.
[0201] Similarly, the crosslinking agent(s) may be selected from
those organic and inorganic compounds well known to those skilled
in the art useful for such purpose, and the phrase "crosslinking
agent", as used herein, includes mixtures of such compounds.
Exemplary organic crosslinking agents include, but are not limited
to, aldehydes, dialdehydes, phenols, substituted phenols, ethers,
and mixtures thereof. Phenol, resorcinol, catechol, phloroglucinol,
gallic acid, pyrogallol, 4,4'-diphenol, 1,3-dihydroxynaphthalene,
1,4-benzoquinone, hydroquinone, quinhydrone, tannin, phenyl
acetate, phenyl benzoate, 1-naphthyl acetate, 2-naphthyl acetate,
phenyl chloracetate, hydroxyphenylalkanols, formaldehyde,
paraformaldehyde, acetaldehyde, propanaldehyde, butyraldehyde,
isobutyraldehyde, valeraldehyde, heptaldehyde, decanal, glyoxal,
glutaraldehyde, terephthaldehyde, hexamethyl-enetetramine,
trioxane, tetraoxane, polyoxymethylene, and divinylether may be
used. Typical inorganic crosslinking agents are polyvalent metals,
chelated polyvalent metals, and compounds capable of yielding
polyvalent metals, including organometallic compounds as well as
borates and boron complexes, and mixtures thereof. In certain
embodiments, the inorganic crosslinking agents include chromium
salts, complexes, or chelates, such as chromium nitrate, chromium
citrate, chromium acetate, chromium propionate, chromium malonate,
chromium lactate, etc.; aluminum salts, such as aluminum citrate,
aluminates, and aluminum complexes and chelates; titanium salts,
complexes, and chelates; zirconium salts, complexes or chelates,
such as zirconium lactate; and boron containing compounds such as
boric acid, borates, and boron complexes. Fluids containing
additives such as those described in U.S. Pat. No. 4,683,068 and
U.S. Pat. No. 5,082,579 may be used.
[0202] As indicated, mixtures of polymeric gel forming material or
gellants may be used. Materials which may be used include water
soluble crosslinkable polymers, copolymers, and terpolymers, such
as polyvinyl polymers, polyacrylamides, cellulose ethers,
polysaccharides, lignosulfonates, ammonium salts thereof, alkali
metal salts thereof, alkaline earth salts of lignosulfonates, and
mixtures thereof. Specific polymers are acrylic acid-acrylamide
copolymers, acrylic acid-methacrylamide copolymers,
polyacrylamides, partially hydrolyzed polyacrylamides, partially
hydrolyzed polymethacrylamides, polyvinyl alcohol, polyvinyl
acetate, polyalkyleneoxides, carboxycelluloses,
carboxyalkylhydroxyethyl celluloses, hydroxyethylcellulose,
galactomannans (e.g., guar gum), substituted galactomannans (e.g.,
hydroxypropyl guar), heteropolysaccharides obtained by the
fermentation of starch-derived sugar (e.g., xanthan gum), ammonium
and alkali metal salts thereof, and mixtures thereof. In certain
embodiments, the water soluble crosslinkable polymers include
hydroxypropyl guar, carboxymethylhydroxypropyl guar, partially
hydrolyzed polyacrylamides, xanthan gum, polyvinyl alcohol, the
ammonium and alkali metal salts thereof, and mixtures thereof.
[0203] The pH of an aqueous fluid which contains a hydratable
polymer can be adjusted if necessary to render the fluid compatible
with a crosslinking agent. In other embodiments, a pH adjusting
material is added to the aqueous fluid after the addition of the
polymer to the aqueous fluid. Typical materials for adjusting the
pH are commonly used acids, acid buffers, and mixtures of acids and
bases. For example, sodium bicarbonate, potassium carbonate, sodium
hydroxide, potassium hydroxide, and sodium carbonate are typical pH
adjusting agents. Acceptable pH values for the fluid may range from
neutral to basic, i.e., from about 5 to about 14. In other
embodiments, the pH is kept neutral or basic, i.e., from about 7 to
about 14. In other embodiments, the pH is between about 8 to about
12.
Breaking Agents
[0204] The breaking agent may be a metal-based oxidizing agent such
as an alkaline earth metal or a transition metal. Exemplary
breaking agents include, without limitation, magnesium peroxide,
calcium peroxide, zinc peroxide, or mixtures and combinations
thereof.
[0205] The term "breaking agent" or "breaker" refers to any
chemical that is capable of reducing the viscosity of a gelled
fluid. As described above, after a fracturing fluid is formed and
pumped into a subterranean formation, it is generally desirable to
convert the highly viscous gel to a lower viscosity fluid. This
allows the fluid to be easily and effectively removed from the
formation and to allow desired material, such as oil or gas, to
flow into the well bore. This reduction in viscosity of the
treating fluid is commonly referred to as "breaking". Consequently,
the chemicals used to break the viscosity of the fluid is referred
to as a breaking agent or a breaker.
[0206] There are various methods available for breaking a
fracturing fluid or a treating fluid. Typically, fluids break after
the passage of time and/or prolonged exposure to high temperatures.
However, it is desirable to be able to predict and control the
breaking within relatively narrow limits. Mild oxidizing agents are
useful as breakers when a fluid is used in a relatively high
temperature formation, although formation temperatures of
300.degree. F. (149.degree. C.) or higher will generally break the
fluid relatively quickly without the aid of an oxidizing agent.
[0207] Examples of inorganic breaking agents for use in this
invention include, but are not limited to, persulfates,
percarbonates, perborates, peroxides, perphosphates, permanganates,
etc. Specific examples of inorganic breaking agents include, but
are not limited to, alkaline earth metal persulfates, alkaline
earth metal percarbonates, alkaline earth metal perborates,
alkaline earth metal peroxides, alkaline earth metal perphosphates,
zinc salts of peroxide, perphosphate, perborate, and percarbonate,
and so on. Additional suitable breaking agents are disclosed in
U.S. Pat. Nos. 5,877,127; 5,649,596; 5,669,447; 5,624,886;
5,106,518; 6,162,766; and 5,807,812, incorporated herein by
reference. In some embodiments, an inorganic breaking agent is
selected from alkaline earth metal or transition metal-based
oxidizing agents, such as magnesium peroxides, zinc peroxides, and
calcium peroxides.
[0208] In addition, enzymatic breakers may also be used in place of
or in addition to a non-enzymatic breaker. Examples of suitable
enzymatic breakers such as guar specific enzymes, alpha and beta
amylases, amyloglucosidase, aligoglucosidase, invertase, maltase,
cellulase, and hemi-cellulase are disclosed in U.S. Pat. Nos.
5,806,597 and 5,067,566, incorporated herein by reference.
[0209] A breaking agent or breaker may be used "as is" or be
encapsulated and activated by a variety of mechanisms including
crushing by formation closure or dissolution by formation fluids.
Such techniques are disclosed, for example, in U.S. Pat. Nos.
4,506,734; 4,741,401; 5,110,486; and 3,163,219, incorporated herein
by reference.
Aggregating or Zeta Potential Altering Compositions
[0210] Amine-Phosphate Reaction Product Aggregating or Zeta
Potential Altering Compositions
[0211] Amines
[0212] Suitable amines include, without limitation, any amine that
is capable of reacting with a suitable phosphate ester 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, indolizine
and alkyl indolizines or mixtures of alkyl indolizines, 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.
[0213] Phosphate Compounds
[0214] Suitable phosphate compounds include, without limitation,
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), polymers thereof, 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 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 carbenyl 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.
[0215] Polymeric Amine Zeta Potential Aggregating Compositions
[0216] Suitable amines capable of forming a deformable coating on a
solid particles, surfaces, and/or materials include, without
limitation, heterocyclic aromatic amines, substituted heterocyclic
aromatic amines, poly vinyl heterocyclic aromatic amines,
co-polymers of vinyl heterocyclic aromatic amine and non amine
polymerizable monomers (ethylenically unsaturated mononers and
diene monomers), or mixtures or combinations thereof, where the
substituents of the substituted heterocyclic aromatic amines are
carbyl groups 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. In certain embodiments, 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, indolizine and
alkyl indolizines or mixtures of alkyl indolizines, 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. In certain embodiments, the poly vinyl
heterocyclic amines include, without limitation, polymers and
copolymers of vinyl pyridine, vinyl substituted pyridine, vinyl
indolizines, vinyl substituted indolizines, vinyl pyrrole, vinyl
substituted pyrroles, vinyl piperidine, vinyl substituted
piperidines, vinyl pyrrolidine, vinyl substituted pyrrolidines,
vinyl indole, vinyl substituted indoles, vinyl imidazole, vinyl
substituted imidazole, vinyl quinoline, vinyl substituted
quinoline, vinyl isoquinoline, vinyl substituted isoquinoline,
vinyl pyrazine, vinyl substituted pyrazine, vinyl quinoxaline,
vinyl substituted quinoxaline, vinyl acridine, vinyl substituted
acridine, vinyl pyrimidine, vinyl substituted pyrimidine, vinyl
quinazoline, vinyl substituted quinazoline, or mixtures and
combinations thereof. In certain embodiments, the heterocyclic
aromatic amines comprise HAP.TM.-310 available from Vertellus
Specialties Inc.
[0217] Amine Component and Amine Component and Amine-Phosphate
Reaction Product Aggregating Compositions
[0218] Suitable amines for the amine component include, without
limitation, an 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 1 and 40 carbon atoms and the required hydrogen atoms to
satisfy the valence, where at least R.sup.1 or R.sup.2 is a
nitrogen containing heterocycle, 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, 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, indolizine and alkyl indolizines or mixture of
alkyl indolizinesindole 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. In certain
embodiments, the amines of the amine components comprise alkyl
pyridines.
[0219] Amine Polymeric Zeta Potential Aggregating Compositions
[0220] 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 mixtures thereof. 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 indolizines, vinyl substituted
indolizines, vinyl quinolines or substituted vinyl quinolines,
vinyl anilines or substituted vinyl anilines, vinyl piperidines or
substituted vinyl piperidines, vinyl pyrrolidines 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 include 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.
[0221] Examples of vinyl amine polymers covered in Weatherford U.S.
Pat. No. 8,466,094.
[0222] From the claims: 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
optionally a reaction product of an amine and a
phosphate-containing compound.
[0223] 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 mixtures thereof. 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 pyrrolidines 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.
[0224] For further details on the aggregating compositions used in
this invention the reader is referred to U.S. Pat. Nos. 7,392,847;
7,956,017; 8,466,094; and 8,871,694; and United States Pub. Nos.
20100212905, and 20130075100.
[0225] Coacervates Aggregating Compositions
[0226] The surfactant which is oppositely charged from the polymer
is sometimes called herein the "counterionic surfactant." By this
we mean a surfactant having a charge opposite that of the
polymer.
[0227] Suitable cationic polymers include polyamines, quaternary
derivatives of cellulose ethers, quaternary derivatives of guar,
homopolymers and copolymers of at least 20 mole percent dimethyl
diallyl ammonium chloride (DMDAAC), homopolymers and copolymers of
methacrylamidopropyl trimethyl ammonium chloride (MAPTAC),
homopolymers and copolymers of acrylamidopropyl trimethyl ammonium
chloride (APTAC), homopolymers and copolymers of
methacryloyloxyethyl trimethyl ammponium chloride (METAC),
homopolymers and copolymers of acryloyloxyethyl trimethyl ammonium
chloride (AETAC), homopolymers and copolymers of
methacryloyloxyethyl trimethyl ammonium methyl sulfate (METAMS),
and quaternary derivatives of starch.
[0228] Suitable anionic polymers include homopolymers and
copolymers of acrylic acid (AA), homopolymers and copolymers of
methacrylic acid (MAA), homopolymers and copolymers of
2-acrylamido-2-methylpropane sulfonic acid (AMPSA), homopolymers
and copolymers of N-methacrylamidopropyl N,N-dimethyl amino acetic
acid, N-acrylamidopropyl N,N-dimethyl amino acetic acid,
N-methacryloyloxyethyl N,N-dimethyl amino acetic acid, and
N-acryloyloxyethyl N,N-dimethyl amino acetic acid.
[0229] Anionic surfactants suitable for use with the cationic
polymers include alkyl, aryl or alkyl aryl sulfates, alkyl, aryl or
alkyl aryl carboxylates or alkyl, aryl or alkyl aryl sulfonates.
Preferably, the alkyl moieties have about 1 to about 18 carbons,
the aryl moieties have about 6 to about 12 carbons, and the alkyl
aryl moieties have about 7 to about 30 carbons. Exemplary groups
would be propyl, butyl, hexyl, decyl, dodecyl, phenyl, benzyl and
linear or branched alkyl benzene derivatives of the carboxylates,
sulfates and sulfonates. Included are alkyl ether sulphates,
alkaryl sulphonates, alkyl succinates, alkyl sulphosuccinates,
N-alkoyl sarcosinates, alkyl phosphates, alkyl ether phosphates,
alkyl ether carboxylates, alpha-olefin sulphonates and acyl methyl
taurates, especially their sodium, magnesium ammonium and mono-,
di- and triethanolamine salts. The alkyl and acyl groups generally
contain from 8 to 18 carbon atoms and may be unsaturated. The alkyl
ether sulphates, alkyl ether phosphates and alkyl ether
carboxylates may contain from one to 10 ethylene oxide or propylene
oxide units per molecule, and preferably contain 2 to 3 ethylene
oxide units per molecule. Examples of suitable anionic surfactants
include sodium lauryl sulphate, sodium lauryl ether sulphate,
ammonium lauryl sulphosuccinate, ammonium lauryl sulphate, ammonium
lauryl ether sulphate, sodium dodecylbenzene sulphonate,
triethanolamine dodecylbenzene sulphonate, sodium cocoyl
isethionate, sodium lauroyl isethionate, and sodium N-lauryl
sarcosinate.
[0230] Cationic surfactants suitable for use with the anionic
polymers include quaternary ammonium surfactants of the formula
X.sup.-N.sup.+R.sup.1R.sup.2R.sup.3 where R.sup.1, R.sup.2, and
R.sup.3 are independently selected from hydrogen, an aliphatic
group of from about 1 to about 22 carbon atoms, or aromatic, aryl,
an alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, or alkylaryl
group having from about 1 to about 22 carbon atoms; and X is an
anion selected from halogen, acetate, phosphate, nitrate, sulfate,
alkylsulfate radicals (e.g., methyl sulfate and ethyl sulfate),
tosylate, lactate, citrate, and glycolate. The aliphatic groups may
contain, in addition to carbon and hydrogen atoms, ether linkages,
and other groups such as hydroxy or amino group substituents (e.g.,
the alkyl groups can contain polyethylene glycol and polypropylene
glycol moieties). The longer chain aliphatic groups, e.g., those of
about 12 carbons, or higher, can be saturated or unsaturated. More
preferably, R.sup.1 is an alkyl group having from about 12 to about
18 carbon atoms; R.sup.2 is selected from H or an alkyl group
having from about 1 to about 18 carbon atoms; R.sup.3 and R.sup.4
are independently selected from H or an alkyl group having from
about 1 to about 3 carbon atoms; and X is as described above.
[0231] Suitable hydrophobic alcohols having 6-23 carbon atoms are
linear or branched alkyl alcohols of the general formula
C.sub.MH.sub.2M+2-N(OH).sub.N, where M is a number from 6-23, and N
is 1 when M is 6-12, but where M is 13-23, N may be a number from 1
to 3. Our most preferred hydrophobic alcohol is lauryl alcohol, but
any linear monohydroxy alcohol having 8-15 carbon atoms is also
preferable to an alcohol with more or fewer carbon atoms.
[0232] By a gel promoter we mean a betaine, a sultaine or
hydroxysultaine, or an amine oxide. Examples of betaines include
the higher alkyl betaines such as coco dimethyl carboxymethyl
betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl
alphacarboxyethyl betaine, cetyl dimethyl carboxymethyl betaine,
cetyl dimethyl betaine, lauryl bis-(2-hydroxyethyl)carboxymethyl
betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl
bis-(2-hydroxypropyl)alphacarboxyethyl betaine, coco dimethyl
sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl
bis-(2-hydroxyethyl)sulfopropyl betaine, amidobetaines and
amidosulfobetaines (wherein the RCONH(CH.sub.2).sub.3 radical is
attached to the nitrogen atom of the betaine, oleyl betaine, and
cocamidopropyl betaine. Examples of sultaines and hydroxysultaines
include materials such as cocamidopropyl hydroxysultaine.
[0233] By a Zeta potential having an absolute value of at least 20
we mean a Zeta potential having a value of +20 of higher or -20 or
lower.
[0234] Amphoteric surfactants suitable for use with either cationic
polymers or anionic polymers include those surfactants broadly
described as derivatives of aliphatic secondary and tertiary amines
in which the aliphatic radical can be straight or branched chain
and wherein one of the aliphatic substituents contains from about 8
to about 18 carbon atoms and one contains an anionic water
solubilizing group such as carboxy, sulfonate, sulfate, phosphate,
or phosphonate. Suitable amphoteric surfactants include derivatives
of aliphatic secondary and tertiary amines in which the aliphatic
radical can be straight or branched chain and wherein one of the
aliphatic aliphatic substituents contains from about 8 to about 18
carbon atoms and one contains an anionic water solubilizing group,
e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
Examples of compounds falling within this definition are sodium
3-dodecylaminopropionate, and sodium 3-dodecylaminopropane
sulfonate.
[0235] Suitable amine oxides include cocoamidopropyl dimethyl amine
oxide and other compounds of the formula
R.sup.1R.sup.2R.sup.3N.fwdarw.O wherein R.sup.3 is a hydrocarbyl or
substituted hydrocarbyl having from about 8 to about 30 carbon
atoms, and R.sup.1 and R.sup.2 are independently hydrogen, a
hydrocarbyl or substituted hydrocarbyl having up to 30 carbon
atoms. Preferably, R.sup.3 is an aliphatic or substituted aliphatic
hydrocarbyl having at least about 12 and up to about 24 carbon
atoms. More preferably R.sup.3 is an aliphatic group having at
least about 12 carbon atoms and having up to about 22, and most
preferably an aliphatic group having at least about 18 and no more
than about 22 carbon atoms.
[0236] Suitable phosphorus-containing compounds suitable for use in
the invention include, without limitation, phosphates or phosphate
equivalents or mixtures or combinations thereof. Suitable
phosphates include, without limitation, mono-alkali metal
phosphates (PO(OH)(OM), where M is Li, Na, K, Rd, or Cs), di-alkali
metal phosphates (PO(OH)(OM).sub.2, where each M is the same or
different and is Li, Na, K, Rd, or Cs) such as dipotassium
phosphate (PO(OH)(OK).sub.2) and disodium phosphate,
(PO(OH)(ONa).sub.2), tri-alkali metal phosphates (PO(OM).sub.3,
where each M is the same or different and is Li, Na, K, Rd, or Cs)
such as trisodium phosphate (PO(ONa).sub.3) and tripotassium
phosphate (PO(OK).sub.3), carbyl phosphates (PO(OR1)(OM).sub.2,
where R.sup.1 is a carbyl group and M is H, Li, Na, K, Rd, and/or
Cs), dicarbyl phosphates (PO(OR1)(OR.sup.2)(OM), where R.sup.1 and
R.sup.2 are the same or different carbyl groups and M is H, Li, Na,
K, Rd, or Cs), tricarbyl phosphates (PO(OR1)(OR.sup.2)(OR.sup.3),
where R.sup.1, R.sup.2, and R.sup.3 are the same or different
carbyl groups), or mixtures or combinations thereof.
[0237] Suitable carbyl group include, without limitations, carbyl
group having between about 3 and 40 carbon atoms, where one or more
of the carbon atoms can be replaced with a hetero atom selected
from the group consisting of oxygen and nitrogen, with the
remainder of valences comprising hydrogen or a mono-valent group
such as a halogen, an amide (--NHCOR), an alkoxide (OR), or the
like, where R is a carbyl group. The carbyl group can be an alkyl
group, an alkenyl group, an aryl group, an alkaaryl group, an
aryalkyl group, or mixtures or combinations thereof, i.e., each
carbyl group in the phosphate can be the same or different. In
certain embodiments, the carbyl group has between about 3 and about
20, where one or more of the carbon atoms can be replaced with a
hetero atom selected from the group consisting of oxygen and
nitrogen, with the remainder of valences comprising hydrogen or a
mono-valent group such as a halogen, an amide (--NHCOR), an
alkoxide (--OR), or the like, where R is a carbyl group. In certain
embodiments, the carbyl group has between about 3 and about 16,
where one or more of the carbon atoms can be replaced with a hetero
atom selected from the group consisting of oxygen and nitrogen,
with the remainder of valences comprising hydrogen or a mono-valent
group such as a halogen, an amide (--NHCOR), an alkoxide (--OR), or
the like, where R is a carbyl group. In certain embodiments, the
carbyl group has between about 3 and about 12, where one or more of
the carbon atoms can be replaced with a hetero atom selected from
the group consisting of oxygen and nitrogen, with the remainder of
valences comprising hydrogen or a mono-valent group such as a
halogen, an amide (--NHCOR), an alkoxide (--OR), or the like, where
R is a carbyl group. In certain embodiments, the carbyl group has
between about 4 and about 8, where one or more of the carbon atoms
can be replaced with a hetero atom selected from the group
consisting of oxygen and nitrogen, with the remainder of valences
comprising hydrogen or a mono-valent group such as a halogen, an
amide (--NHCOR), an alkoxide (--OR), or the like, where R is a
carbyl group.
[0238] Suitable tri-alkyl phosphates include, without limitations,
alkyl group having from about 3 to about 20 carbon atoms, where one
or more of the carbon atoms can be replaced with a hetero atom
selected from the group consisting of oxygen and nitrogen, with the
remainder of valences comprising hydrogen or a mono-valent group
such as a halogen, an amide (--NHCOR), an alkoxide (--OR), or the
like, where R is a carbyl group. In certain embodiments, the
tri-alkyl phosphate includes alkyl groups having from about 4 to
about 12 carbon atoms, where one or more of the carbon atoms can be
replaced with a hetero atom selected from the group consisting of
oxygen and nitrogen, with the remainder of valences comprising
hydrogen or a mono-valent group such as a halogen, an amide
(--NHCOR), an alkoxide (OR), or the like, where R is a carbyl
group. In other embodiments, the tri-alkyl phosphate includes alkyl
groups having from about 4 to about 8 carbon atoms, where one or
more of the carbon atoms can be replaced with a hetero atom
selected from the group consisting of oxygen and nitrogen, with the
remainder of valences comprising hydrogen or a mono-valent group
such as a halogen, an amide (--NHCOR), an alkoxide (OR), or the
like, where R is a carbyl group. Such phosphates can be produced by
reacting a phosphate donor such as phosphorus pentoxide and a
mixture of alcohols in desired proportions.
Aggregation Coating Stabilizers and/or Strengtheners
[0239] Suitable aggregation coating stabilizer and/or strengtheners
include, without limitation, inorganic crosslinking agents, organic
crosslinking agents, and mixtures or combinations thereof.
[0240] Suitable inorganic crosslinking agents includes, without
limitation, metal compounds capable of forming a network of metal
complexes within the coating to stabilize, consolidate and/or
strengthen the coating. The metal compounds are selected from the
group consisting of groups 2-17 metal compounds. The group 2 metal
compounds include compounds of Be, Mg, Ca, Sr, and Ba. The group 3
metal compounds include compounds of Sc, Y, La and Ac. The group 4
metal compounds include compounds of Ti, Zr, Hf, Ce, and Th. The
group 5 metal compounds include compounds of V, Nb, Ta, and Pr. The
group 6 metal compounds include compounds of Cr, Mo, W, Nd, and U.
The group 7 metal compounds include compounds of Mn, Tc, Re, and
Pm. The group 8 metal compounds include compounds of Fe, Ru, Os,
and Sm. The group 9 metal compounds include compounds of Co, Rh,
Ir, and Eu. The group 10 metal compounds include compounds of Ni,
Pd, Pt, and Gd. The group 11 metal compounds include compounds of
Cu, Ag, Au, and Tb. The group 12 metal compounds include compounds
of Zn, Cd, Hg, and Dy. The group 13 metal compounds include
compounds of Al, Ga, In, Tl, and Ho. The group 14 metal compounds
include compounds of Si, Ge, Sn, Pb, and Er. The group 15 metal
compounds include compounds of As, Sb, Bi, and Tm. The group 16
metal compounds include compounds of Yb. The group 17 metal
compounds include compounds of Lu. Alternatively, the metal
compounds includes alkaline earth metal compounds, poor metal
compounds, transition metal compounds, lanthanide metal compounds,
actinide metal compounds, and mixtures or combinations thereof. The
metal compounds may be in the form of halides, carbonates, oxides,
sulfates, sulfites, phosphates, phosphites, nitrates, nitrites,
carboxylates (formates, acetates, propionates, butionates,
citrates, oxylates, or higher carboxylates),
[0241] Suitable organic crosslinking agents include, without
limitation, di-glycidyl ethers, tri-glycidyl ethers,
carbyldihalides, bisphenol A, di-isocynates, tri-isocynates, diacyl
azides, cyanuaric chloride, diacids, polyacids, imidylated di and
poly carboxylic acids, anhydrides, carbonates, diepoxides,
dialdehydes, diisothiocyantes, divinylsulfones, such as other
similar organic crosslinking agents, and mixtures or combinations
thereof.
[0242] Suitable tackifying compounds and process are disclosed in
U.S. Pat. Nos. 5,853,048; 7,258,170 B2 and US 2005/0277554 A1.
Tackifying compositions or bonding agents include polyacrylate
ester polymers, polyamide, phenolic and epoxy. Tackifying compounds
may be produced by the reaction of a polyacid with a multivalent
ion such as calcium, aluminum, iron or the like. Similarly various
polyorganophosphates, polyphosphonate, polysulfate,
polycarboxylates or polysilicates may be reacted with a multivalent
ion to yield a tackifying compound. In certain embodiment, the
tackifying agent is the condensation reaction ofpolyacids and
polyamines. C36 dibasic acids, trimer acids, synthetic acids
produced from fatty acids, maleic anhydride and acrylic acids are
examples of polyacids. Polyamines can comprise ethylenediamine,
diethylentriamine, triethylenetetramine, tetraethylenepentamine,
N-(2-aminoethyl)piperazine and the like.
Solid Materials and Proppants
[0243] Suitable solid materials and/or proppants capable of being
pre-treated or treated with the aggregating 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, any other
solid material that does or may find use in downhole applications,
treated analogs thereof, where solid materials and/or proppants are
treated with the aggregating compositions of this invention, 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.
[0244] Examples of suitable proppants include, but are not limited
to, quartz sand grains, glass and ceramic beads, walnut shell
fragments, aluminum pellets, nylon pellets, and the like. Proppants
are typically used in concentrations between about 1 to 8 lbs. per
gallon of a fracturing fluid, although higher or lower
concentrations may also be used as desired.
[0245] Sand, resin-coated sand, and ceramic particles are the most
commonly used proppants, though the literature, for instance U.S.
Pat. No. 4,654,266, incorporated herein by reference, also mentions
the used of walnut hull fragments coated with some bonding
additives, metallic shots, or metal-coated beads--nearly spherical
but having a passageways to improve their conductibility.
[0246] The proppant conductivity is affected principally by two
parameters, the proppant pack width and the proppant pack
permeability. To improve fracture proppant conductivity, typical
approaches include high large diameter proppants. More generally,
the most common approaches to improve proppant fracture performance
include high strength proppants, large diameter proppants, high
proppant concentrations in the proppant pack to obtain wider
propped fractures, conductivity enhancing materials such as
breakers, flow-back aides, fibers and other material that
physically alter proppant packing, and use of non-damaging
fracturing fluids such as gelled oils, viscoelastic surfactant
based fluids, foamed fluids or emulsified fluids. It is also
recognized that grain size, grain-size distribution, quantity of
fines and impurities, roundness and sphericity and proppant density
have an impact on fracture conductivity.
[0247] As mentioned above, the main function of the proppant is to
keep the fracture open by overcoming the in-situ stress. Where the
proppant strength is not high enough, the closure stress crushes
the proppant, creating fines and reducing the conductivity. Sand is
typically suitable for closure stresses of less than about 6000 psi
(41 MPa), resin-coated sand may be used up to about 8000 psi (55
MPa). Intermediate-strength proppant typically consists of fused
ceramic or sintered-bauxite and is used for closure stresses
ranging between 5000 psi and 10000 psi (34 MPa to 69 MPa).
High-strength proppant, consisting of sintered-bauxite with large
amounts of corundum is used at closure stresses of up to about
14000 psi (96 MPa).
[0248] Permeability of a propped fracture increases as the square
of the grain diameter. However, larger grains are often more
susceptible to crush, have more placement problems and tend to be
more easily invaded by fines. As the result, the average
conductivity over the life of a well may be actually higher with
smaller proppants.
[0249] It should be recognized that the proppant itself is may be
of any shape including irregular shapes, essentially spherical
shapes, elongated shapes, etc. Adding fibers or fiber-like products
to the fluids may contribute to a reduction of the proppant
flowback and consequently to a better packing of the proppant
islands in the fracture, as the fibers will adhere to the islands
because the islands include an amount of proppants coated with an
aggregating composition of this invention or treated with an
aggregating composition and a coating crosslinking composition.
Additionally, the fibers may prevent or reduce fine migrations and
consequently, prevent or reduce a reduction of the proppant
conductivity by forming new types of proppant islands that will
lead to higher formation conductivity.
Fibers and Organic Particulate Materials
[0250] Non-Erodible Fibers
[0251] Suitable non soluble or non erodible fibers include, without
limitation, natural fibers, synthetic fibers, or mixtures and
combinations thereof. Exemplary examples of natural fibers include,
without limitation, abaca, cellulose, wool such as alpaca wool,
cashmere wool, mohair, or angora wool, camel hair, coir, cotton,
flax, hemp, jute, ramie, silk, sisal, byssus fibers, chiengora
fibers, muskox wool, yak wool, rabbit hair, kapok, kenaf, raffia,
bamboo, Pifia, asbestos fibers, glass fibers, cellulose fibers,
wood pulp fibers, treated analogs thereof, or mixtures and
combinations thereof. Exemplary examples of synthetic fibers
include, without limitation, regenerated cellulose fibers,
cellulose acetate fibers, polyester fibers, aramid fibers, acrylic
fibers, fibre optic fibers, polyamide and polyester fibers,
polyethylene fibers, polypropylene fibers, acrylic fibers, aramid
fibers, silk fibers, azlon fibers, BAN-LON.RTM. fibers (registered
trademark of Joseph Bancroft & Sons Company), basalt fiber,
carbon fiber, CELLIANT.RTM. fiber (registered trademark
ofHologenix, LLC), cellulose acetate fiber, cellulose triacetate
fibers, CORDURA.RTM. fibers (registered trademark of INVISTA, a
subsidiary of privately owned Koch Industries, Inc.), crimplene (a
polyester) fibers, cuben fibers, cuprammonium rayon fibers, dynel
fibers, elasterell fibers, elastolefin fibers, glass fibers, GOLD
FLEX.RTM. fibers (registered trademark of Honeywell), INNEGRA S.TM.
fibers (brandname of Innegra Technologies LLC), aramid fibers such
as KEVLAR.RTM. fibers (registered trademark of DuPont), KEVLAR.RTM.
KM2 fibers (registered trademark of DuPont), LASTOL.RTM. fibers
(registered trademark of DOW Chemicals Company), Lyocell fibers, M5
fibers, modacrylic fibers, Modal fibers, NOMEX.RTM. fibers
(registered trademark ofDuPont), nylon fibers such as nylon 4
fibers, nylon 6 fibers, nylon 6-6 fibers, polyolefin fibers,
poly(p-phenylene sulfide) fibers, polyacrylonitrile fibers,
polybenzimidazole fibers, polydioxanone fibers, polyester fibers,
qiana fibers, rayon fibers, polyvinylidene chloride fibers such as
Saran fibers, ofpoly(trimethylene terephthalate) fibers such as
Sorona fibers, spandex or elastane fibers, Taklon fibers, Technora
fibers, THINSULATE.RTM. fibers (registered trademark of 3M),
Twaron.TM. fibers (brandname ofTeij in Aramid),
ultra-high-molecular-weight polyethylene fibers, syndiotactic
polypropylene fibers, isotactic polypropylene fibers,
polyvinylalcohol fibers, cellulose xanthate fibers,
poly(p-phenylene-2,6-benzobisoxazole) fibers, polyimide fibers,
other synthetic fibers, or mixtures and combinations thereof. These
fibers can additionally or alternatively form a three-dimensional
network, reinforcing the proppant and limiting its flowback.
[0252] Non-Erodible Particles and Fibers
[0253] Suitable solid organic polymeric particulate materials
include, without limitation, polymeric particulate matter derived
from cellulose, acrylic acid, aramides, acrylonitrile, polyamides,
vinylidene, olefins, diolefins, polyester, polyurethane, vinyl
alcohol, and vinyl chloride, may be used. Preferred compositions,
assuming the required reactivity and/or decomposition
characteristics may be selected from rayon, acetate, triacetate,
cotton, wool (cellulose group); nylon, acrylic, modacrylic,
nitrile, polyester, saran, spandex, vinyon, olefin, vinyl,
(synthetic polymer group); azlon, rubber (protein and rubber
group), and mixtures thereof. Polyester and polyamide particles of
sufficient molecular weight, such as from Dacron.RTM. and nylon,
respectively, and mixtures thereof, are most preferred. Again,
composite particles, comprising natural and/or synthetic materials
of appropriate characteristics, may be employed. For example, a
suitable composite particle might comprise a core and sheath
structure where the sheath material and the core material degrade
over different desired periods of time. The compounds or
compositions employed as organic polymeric material according to
the invention need not be pure, and commercially available
materials containing various additives, fillers, etc. or having
coatings may be used, so long as such components do not interfere
with the required activity. The organic polymeric particulate
material level, i.e., concentration, provided initially in the
fluid may range from 0.02 percent up to about 10 percent by weight
of the fluid. Most preferably, however, the concentration ranges
from about 0.02 percent to about 5.0 percent by weight of
fluid.
[0254] Particle size and shape, while important, may be varied
considerably, depending on timing and transport considerations. In
certain embodiments, if irregular or spherical particles of the
organic polymer are used, particle size may range from 80 mesh to
2.5 mesh (Tyler), preferably from 60 mesh to 3 mesh. Fibers and/or
platelets of the specified polymeric materials are preferred for
their mobility and transfer aiding capability. In the case of
fibers of the organic polymer, the fibers employed according to the
invention may also have a wide range of dimensions and properties.
As employed herein, the term "fibers" refers to bodies or masses,
such as filaments, of natural or synthetic material(s) having one
dimension significantly longer than the other two, which are at
least similar in size, and further includes mixtures of such
materials having multiple sizes and types. In other embodiments,
individual fiber lengths may range upwardly from about 1
millimeter. Practical limitations of handling, mixing, and pumping
equipment in wellbore applications, currently limit the practical
use length of the fibers to about 100 millimeters. Accordingly, in
other embodiments, a range of fiber length will be from about 1 mm
to about 100 mm or so. In yet other embodiments, the length will be
from at least about 2 mm up to about 30 mm. Similarly, fiber
diameters will preferably range upwardly from about 5 microns. In
other embodiments, the diameters will range from about 5 microns to
about 40 microns. In other embodiments, the diameters will range
from about 8 microns to about 20 microns, depending on the modulus
of the fiber, as described more fully hereinafter. A ratio of
length to diameter (assuming the cross section of the fiber to be
circular) in excess of 50 is preferred. However, the fibers may
have a variety of shapes ranging from simple round or oval
cross-sectional areas to more complex shapes such as trilobe,
figure eight, star-shape, rectangular cross-sectional, or the like.
Preferably, generally straight fibers with round or oval cross
sections will be used. Curved, crimped, branched, spiral-shaped,
hollow, fibrillated, and other three dimensional fiber geometries
may be used. Again, the fibers may be hooked on one or both ends.
Fiber and platelet densities are not critical, and will preferably
range from below 1 to 4 g/cm.sup.3 or more.
[0255] Those skilled in the art will recognize that a dividing line
between what constitute "platelets", on one hand, and "fibers", on
the other, tends to be arbitrary, with platelets being
distinguished practically from fibers by having two dimensions of
comparable size both of which are significantly larger than the
third dimension, fibers, as indicated, generally having one
dimension significantly larger than the other two, which are
similar in size. As used herein, the terms "platelet" or
"platelets" are employed in their ordinary sense, suggesting
flatness or extension in two particular dimensions, rather than in
one dimension, and also is understood to include mixtures of both
differing types and sizes. In general, shavings, discs, wafers,
films, and strips of the polymeric material(s) may be used.
Conventionally, the term "aspect ratio" is understood to be the
ratio of one dimension, especially a dimension of a surface, to
another dimension. As used herein, the phrase is taken to indicate
the ratio of the diameter of the surface area of the largest side
of a segment of material, treating or assuming such segment surface
area to be circular, to the thickness of the material (on average).
Accordingly, the platelets utilized in the invention will possess
an average aspect ratio of from about 10 to about 10,000. In
certain embodiments the average aspect ration is from 100 to 1000.
In other embodiments, the platelets will be larger than 5 microns
in the shortest dimension, the dimensions of a platelet which may
be used in the invention being, for example, 6 mm.times.2
mm.times.15 mm.
[0256] In a particularly advantageous aspect of the invention,
particle size of the organic polymeric particulate matter may be
managed or adjusted to advance or retard the reaction or
degradation of the gelled suspension in the fracture. Thus, for
example, of the total particulate matter content, 20 percent may
comprise larger particles, e.g., greater than 100 microns, and 80
percent smaller, say 80 percent smaller than 20 micron particles.
Such blending in the gelled suspension may provide, because of
surface area considerations, a different time of completion of
reaction or decomposition of the particulate matter, and hence the
time of completion of gel decomposition or breaking, when compared
with that provided by a different particle size distribution.
[0257] The solid particulate matter, e.g., fibers, or fibers and/or
platelet, containing fluid suspensions used in the invention may be
prepared in any suitable manner or in any sequence or order. Thus,
the suspension may be provided by blending in any order at the
surface, and by addition, in suitable proportions, of the
components to the fluid or slurry during treatment on the fly. The
suspensions may also be blended offsite. In the case of some
materials, which are not readily dispersible, the fibers should be
"wetted" with a suitable fluid, such as water or a wellbore fluid,
before or during mixing with the fracturing fluid, to allow better
feeding of the fibers. Good mixing techniques should be employed to
avoid "clumping" of the particulate matter.
[0258] Erodible Particles and Fibers
[0259] Suitable dissolvable, degradable, or erodible proppants
include, without limitation, water-soluble solids,
hydrocarbon-soluble solids, or mixtures and combinations thereof.
Exemplary examples of water-soluble solids and hydrocarbon-soluble
solids include, without limitation, salt, calcium carbonate, wax,
soluble resins, polymers, or mixtures and combinations thereof.
Exemplary salts include, without limitation, calcium carbonate,
benzoic acid, naphthalene based materials, magnesium oxide, sodium
bicarbonate, sodium chloride, potassium chloride, calcium chloride,
ammonium sulfate, or mixtures and combinations thereof. Exemplary
polymers include, without limitation, polylactic acid (PLA),
polyglycolic acid (PGA), lactic acid/glycolic acid copolymer
(PLGA), polysaccharides, starches, or mixtures and combinations
thereof.
[0260] As used herein, "polymers" includes both homopolymers and
copolymers of the indicated monomer with one or more comonomers,
including graft, block and random copolymers. The polymers may be
linear, branched, star, crosslinked, derivatized, and so on, as
desired. The dissolvable or erodible proppants may be selected to
have a size and shape similar or dissimilar to the size and shape
of the proppant particles as needed to facilitate segregation from
the proppant. Dissolvable, degradable, or erodible proppant
particle shapes can include, for example, spheres, rods, platelets,
ribbons, and the like and combinations thereof. In some
applications, bundles of dissolvable, degradable, or erodible
fibers, or fibrous or deformable materials, may be used.
[0261] The dissolvable, degradable, or erodible proppants may be
capable of decomposing in the water-based fracturing fluid or in
the downhole fluid, such as fibers made of polylactic acid (PLA),
polyglycolic acid (PGA), polyvinyl alcohol (PVOH), and others. The
dissolvable, degradable, or erodible fibers may be made of or
coated by a material that becomes adhesive at subterranean
formation temperatures. The dissolvable, degradable, or erodible
fibers used in one embodiment may be up to 2 mm long with a
diameter of 10-200 microns, in accordance with the main condition
that the ratio between any two of the three dimensions be greater
than 5 to 1. In another embodiment, the dissolvable, degradable, or
erodible fibers may have a length greater than 1 mm, such as, for
example, 1-30 mm, 2-25 mm or 3-18 mm, e.g., about 6 mm; and they
can have a diameter of 5-100 microns and/or a denier of about
0.1-20, preferably about 0.15-6. These dissolvable, degradable, or
erodible fibers are desired to facilitate proppant carrying
capability of the treatment fluid with reduced levels of fluid
viscosifying polymers or surfactants. Dissolvable, degradable, or
erodible fiber cross-sections need not be circular and fibers need
not be straight. If fibrillated dissolvable, degradable, or
erodible fibers are used, the diameters of the individual fibrils
may be much smaller than the aforementioned fiber diameters.
Other Fracturing Fluid Components
[0262] The fracturing fluid may also include ester compound such as
esters ofpolycarboxylic acids. For example, the ester compound may
be an ester of oxalate, citrate, or ethylene diamine tetraacetate.
The ester compound having hydroxyl groups can also be acetylated.
An example of this is that citric acid can be acetylated to form
acetyl triethyl citrate. A presently preferred ester is acetyl
triethyl citrate.
Gases
[0263] Suitable gases for foaming the foamable, ionically coupled
gel composition include, without limitation, nitrogen, carbon
dioxide, or any other gas suitable for use in formation fracturing,
or mixtures or combinations thereof.
Corrosion Inhibitors
[0264] Suitable corrosion inhibitor for use in this invention
include, without limitation: quaternary ammonium salts e.g.,
chloride, bromides, iodides, dimethylsulfates, diethylsulfates,
nitrites, bicarbonates, carbonates, hydroxides, alkoxides, or the
like, or mixtures or combinations thereof; salts of nitrogen bases;
or mixtures or combinations thereof. Exemplary quaternary ammonium
salts include, without limitation, quaternary ammonium salts from
an amine and a quaternarization agent, e.g., alkylchlorides,
alkylbromide, alkyl iodides, alkyl sulfates such as dimethyl
sulfate, diethyl sulfate, etc., dihalogenated alkanes such as
dichloroethane, dichloropropane, dichloroethyl ether,
epichlorohydrin adducts of alcohols, ethoxylates, or the like; or
mixtures or combinations thereof and an amine agent, e.g.,
alkylpyridines, especially, highly alkylated alkylpyridines, alkyl
quinolines, C6 to C24 synthetic tertiary amines, amines derived
from natural products such as coconuts, or the like,
dialkylsubstituted methyl amines, amines derived from the reaction
of fatty acids or oils and polyamines, amidoimidazolines of DETA
and fatty acids, imidazolines of ethylenediamine, imidazolines of
diaminocyclohexane, imidazolines ofaminoethylethylenediamine,
pyrimidine of propane diamine and alkylated propene diamine,
oxyalkylated mono and polyamines sufficient to convert all labile
hydrogen atoms in the amines to oxygen containing groups, or the
like or mixtures or combinations thereof. Exemplary examples of
salts of nitrogen bases, include, without limitation, salts of
nitrogen bases derived from a salt, e.g.: C1l to C8 monocarboxylic
acids such as formic acid, acetic acid, propanoic acid, butanoic
acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid,
2-ethylhexanoic acid, or the like; C2 to C12 dicarboxylic acids, C2
to C12 unsaturated carboxylic acids and anhydrides, or the like;
polyacids such as diglycolic acid, aspartic acid, citric acid, or
the like; hydroxy acids such as lactic acid, itaconic acid, or the
like; aryl and hydroxy aryl acids; naturally or synthetic amino
acids; thioacids such as thioglycolic acid (TGA); free acid forms
of phosphoric acid derivatives of glycol, ethoxylates, ethoxylated
amine, or the like, and aminosulfonic acids; or mixtures or
combinations thereof and an amine, e.g.: high molecular weight
fatty acid amines such as cocoamine, tallow amines, or the like;
oxyalkylated fatty acid amines; high molecular weight fatty acid
polyamines (di, tri, tetra, or higher); oxyalkylated fatty acid
polyamines; amino amides such as reaction products of carboxylic
acid with polyamines where the equivalents of carboxylic acid is
less than the equivalents of reactive amines and oxyalkylated
derivatives thereof; fatty acid pyrimidines; monoimidazolines of
EDA, DETA or higher ethylene amines, hexamethylene diamine (HMDA),
tetramethylenediamine (TMDA), and higher analogs thereof;
bisimidazolines, imidazolines of mono and polyorganic acids;
oxazolines derived from monoethanol amine and fatty acids or oils,
fatty acid ether amines, mono and bis amides of
aminoethylpiperazine; GAA and TGA salts of the reaction products of
crude tall oil or distilled tall oil with diethylene triamine; GAA
and TGA salts of reaction products of dimer acids with mixtures of
poly amines such as TMDA, HMDA and 1,2-diaminocyclohexane; TGA salt
of imidazoline derived from DETA with tall oil fatty acids or soy
bean oil, canola oil, or the like; or mixtures or combinations
thereof.
Other Fracturing Fluid Additives
[0265] The fracturing fluids of this invention may also include
other additives such as pH modifiers, scale inhibitors, carbon
dioxide control additives, paraffin control additives, oxygen
control additives, salt inhibitors, or other additives.
pH Modifiers
[0266] Suitable pH modifiers for use in this invention include,
without limitation, alkali hydroxides, alkali carbonates, alkali
bicarbonates, alkaline earth metal hydroxides, alkaline earth metal
carbonates, alkaline earth metal bicarbonates, rare earth metal
carbonates, rare earth metal bicarbonates, rare earth metal
hydroxides, amines, hydroxylamines (NH.sub.2OH), alkylated hydroxyl
amines (NH.sub.2OR, where R is a carbyl group having from 1 to
about 30 carbon atoms or heteroatoms --O or N), and mixtures or
combinations thereof. Preferred pH modifiers include NaOH, KOH,
Ca(OH).sub.2, CaO, Na.sub.2CO.sub.3, KHCO.sub.3, K.sub.2CO.sub.3,
NaHCO.sub.3, MgO, Mg(OH).sub.2 and mixtures or combinations
thereof. Preferred amines include triethylamine, triproplyamine,
other trialkylamines, bis hydroxyl ethyl ethylenediamine (DGA), bis
hydroxyethyl diamine 1-2 dimethylcyclohexane, or the like or
mixtures or combinations thereof.
Scale Control
[0267] Suitable additives for Scale Control and useful in the
compositions of this invention include, without limitation:
Chelating agents, e.g., Na.sup.+, K.sup.+ or NH salts of EDTA; Na,
K or NH salts of NTA; Na.sup.+, K.sup.+ or NH salts of Erythorbic
acid; Na.sup.+, K.sup.+ or NH salts of thioglycolic acid (TGA);
Na.sup.+, K.sup.+ or NH salts of Hydroxy acetic acid; Na.sup.+,
K.sup.+ or NH salts of Citric acid; Na.sup.+, K.sup.+ or NH salts
of Tartaric acid or other similar salts or mixtures or combinations
thereof. Suitable additives that work on threshold effects,
sequestrants, include, without limitation: Phosphates, e.g., sodium
hexamethylphosphate, linear phosphate salts, salts of
polyphosphoric acid, Phosphonates, e.g., nonionic such as HEDP
(hydroxythylidene diphosphoric acid), PBTC (phosphoisobutane,
tricarboxylic acid), Amino phosphonates of: MEA (monoethanolamine),
NH.sub.3, EDA (ethylene diamine), Bishydroxyethylene diamine,
Bisaminoethylether, DETA (diethylenetriamine), HMDA (hexamethylene
diamine), Hyper homologues and isomers of HMDA, Polyamines of EDA
and DETA, Diglycolamine and homologues, or similar polyamines or
mixtures or combinations thereof; Phosphate esters, e.g.,
polyphosphoric acid esters or phosphorus pentoxide (P.sub.2O.sub.5)
esters of: alkanol amines such as MEA, DEA, triethanol amine (TEA),
Bishydroxyethylethylene diamine; ethoxylated alcohols, glycerin,
glycols such as EG (ethylene glycol), propylene glycol, butylene
glycol, hexylene glycol, trimethylol propane, pentaerythritol,
neopentyl glycol or the like; Tris & Tetra hydroxy amines;
ethoxylated alkyl phenols (limited use due to toxicity problems),
Ethoxylated amines such as monoamines such as MDEA and higher
amines from 2 to 24 carbons atoms, diamines 2 to 24 carbons carbon
atoms, or the like; Polymers, e.g., homopolymers of aspartic acid,
soluble homopolymers of acrylic acid, copolymers of acrylic acid
and methacrylic acid, terpolymers of acylates, AMPS, etc.,
hydrolyzed polyacrylamides, poly malic anhydride (PMA); or the
like; or mixtures or combinations thereof.
Carbon Dioxide Neutralization
[0268] Suitable additives for CO.sub.2 neutralization and for use
in the compositions of this invention include, without limitation,
MEA, DEA, isopropylamine, cyclohexylamine, morpholine, diamines,
dimethylaminopropylamine (DMAPA), ethylene diamine, methoxy
proplyamine (MOPA), dimethylethanol amine, methyldiethanolamine
(MDEA) & oligomers, imidazolines of EDA and homologues and
higher adducts, imidazolines of aminoethylethanolamine (AEEA),
aminoethylpiperazine, aminoethylethanol amine, di-isopropanol
amine, DOW AMP-90.TM., Angus AMP-95, dialkylamines (of methyl,
ethyl, isopropyl), mono alkylamines (methyl, ethyl, isopropyl),
trialkyl amines (methyl, ethyl, isopropyl), bishydroxyethylethylene
diamine (THEED), or the like or mixtures or combinations
thereof.
Paraffin Control
[0269] Suitable additives for Paraffin Removal, Dispersion, and/or
paraffin Crystal Distribution include, without limitation:
Cellosolves available from DOW Chemicals Company; Cellosolve
acetates; Ketones; Acetate and Formate salts and esters;
surfactants composed of ethoxylated or propoxylated alcohols, alkyl
phenols, and/or amines; methylesters such as coconate, laurate,
soyate or other naturally occurring methylesters of fatty acids;
sulfonated methylesters such as sulfonated coconate, sulfonated
laurate, sulfonated soyate or other sulfonated naturally occurring
methylesters of fatty acids; low molecular weight quaternary
ammonium chlorides of coconut oils soy oils or C.sub.10 to C.sub.24
amines or monohalogenated alkyl and aryl chlorides; quanternary
ammonium salts composed of disubstituted (e.g., dicoco, etc.) and
lower molecular weight halogenated alkyl and/or aryl chlorides;
gemini quaternary salts of dialkyl (methyl, ethyl, propyl, mixed,
etc.) tertiary amines and dihalogenated ethanes, propanes, etc. or
dihalogenated ethers such as dichloroethyl ether (DCEE), or the
like; gemini quaternary salts of alkyl amines or amidopropyl
amines, such as cocoamidopropyldimethyl, bis quaternary ammonium
salts of DCEE; or mixtures or combinations thereof. Suitable
alcohols used in preparation of the surfactants include, without
limitation, linear or branched alcohols, specially mixtures of
alcohols reacted with ethylene oxide, propylene oxide or higher
alkyleneoxide, where the resulting surfactants have a range of
HLBs. Suitable alkylphenols used in preparation of the surfactants
include, without limitation, nonylphenol, decylphenol,
dodecylphenol or other alkylphenols where the alkyl group has
between about 4 and about 30 carbon atoms. Suitable amines used in
preparation of the surfactants include, without limitation,
ethylene diamine (EDA), diethylenetriamine (DETA), or other
polyamines. Exemplary examples include Quadrols, Tetrols, Pentrols
available from BASF. Suitable alkanolamines include, without
limitation, monoethanolamine (MEA), diethanolamine (DEA), reactions
products of MEA and/or DEA with coconut oils and acids.
Oxygen Control
[0270] The introduction of water downhole often is accompanied by
an increase in the oxygen content of downhole fluids due to oxygen
dissolved in the introduced water. Thus, the materials introduced
downhole must work in oxygen environments or must work sufficiently
well until the oxygen content has been depleted by natural
reactions. For system that cannot tolerate oxygen, then oxygen must
be removed or controlled in any material introduced downhole. The
problem is exacerbated during the winter when the injected
materials include winterizers such as water, alcohols, glycols,
Cellosolves, formates, acetates, or the like and because oxygen
solubility is higher to a range of about 14-15 ppm in very cold
water. Oxygen can also increase corrosion and scaling. In CCT
(capillary coiled tubing) applications using dilute solutions, the
injected solutions result in injecting an oxidizing environment
(O.sub.2) into a reducing environment (CO.sub.2, H.sub.2S, organic
acids, etc.).
[0271] Options for controlling oxygen content includes: (1)
de-aeration of the fluid prior to downhole injection, (2) addition
of normal sulfides to product sulfur oxides, but such sulfur oxides
can accelerate acid attack on metal surfaces, (3) addition of
erythorbates, ascorbates, diethylhydroxyamine or other oxygen
reactive compounds that are added to the fluid prior to downhole
injection; and (4) addition of corrosion inhibitors or metal
passivation agents such as potassium (alkali) salts of esters of
glycols, polyhydric alcohol ethyloxylates or other similar
corrosion inhibitors. Exemplary examples oxygen and corrosion
inhibiting agents include mixtures of tetramethylene diamines,
hexamethylene diamines, 1,2-diaminecyclohexane, amine heads, or
reaction products of such amines with partial molar equivalents of
aldehydes. Other oxygen control agents include salicylic and
benzoic amides of polyamines, used especially in alkaline
conditions, short chain acetylene diols or similar compounds,
phosphate esters, borate glycerols, urea and thiourea salts of
bisoxalidines or other compound that either absorb oxygen, react
with oxygen or otherwise reduce or eliminate oxygen.
Salt Inhibitors
[0272] Suitable salt inhibitors for use in the fluids of this
invention include, without limitation, Na Minus-Nitrilotriacetamide
available from Clearwater International, LLC of Houston, Tex.
DETAILED DESCRIPTION OF THE DRAWINGS
[0273] Referring now to FIG. 1A, an embodiment of a fracturing
pulse or slug sequence, generally 100, is shown to include a pad
stage 102 having a pad duration t.sub.pad, a proppant placement
stage 104 having a proppant placement duration t.sub.pp, and a
tail-in stage 106 having a tail-in duration t.sub.t. The proppant
placement stage 104 includes four sub-stages 108, 110, 112, and
114, each sub-stage 108, 110, 112, and 114 include two
proppant-free fluid pulses 108a&b, 110a&b, 112a&b, and
114a&b and two proppant-containing fluid pulses 108c&d,
110c&d, 112c&d, and 114c&d. Each sub-stage 108, 110,
112, and 114 is described by a pulse cycle duration t.sub.pcycle.
The pulse cycle duration t.sub.pcycle includes a
proppant-containing fluid pulse duration t.sub.pcp and a
proppant-free fluid pulse duration t.sub.pfp, where the durations
t.sub.pcycle, t.sub.pcp, and t.sub.pfp may be the same or different
for each sub-stage 108, 110, 112, and 114 and the durations
t.sub.pcp and t.sub.pfp in each cycle may be the same or
different.
[0274] Referring now to FIG. 1B, another embodiment of a fracturing
pulse or slug sequence, generally 120, is shown to include a pad
stage 122 having a pad duration t.sub.pad, a proppant placement
stage 124 having a proppant placement duration t.sub.pp, and a
tail-in stage 126 having a tail-in duration t.sub.t. The proppant
placement stage 124 includes four sub-stages 128, 130, 132, and
134, each sub-stage 128, 130, 132, and 134 include a plurality of
sinusoidal proppant-free fluid pulses 128a-c, 130a-c, 132a-c, and
134a-c and a plurality of sinusoidal proppant-containing fluid
pulses 128e-g, 130e-g, 132e-g, and 134e-g. Each sub-stage 128, 130,
132, and 134 is described by a sinusoidal pulse cycle duration
t.sub.pcycle. The pulse cycle durations t.sub.pcycle may be the
same or different for each sub-stage 128, 130, 132, and 134 and
durations of the sinusoidal proppant-containing phases and
durations of the sinusoidal proppant-free phases in each cycle may
be the same or different.
[0275] Referring now to FIG. 1C, another embodiment of a fracturing
pulse or slug sequence, generally 140, is shown to include a pad
stage 142 having a pad duration t.sub.pad, a proppant placement
stage 144 having a proppant placement duration t.sub.pp, and a
tail-in stage 146 having a tail-in duration t.sub.t. The proppant
placement stage 144 is shown here as a continuous increasing volume
ramp. The ramp 144 includes a plurality of proppant-free fluid
pulses 144a-h and a plurality of proppant-containing fluid pulses
104i-o. Each of the proppant-containing fluid pulses 104i-o
comprises an aggregating composition or an aggregating composition
and a coating crosslinking composition pulse, which may be centered
in the proppant-containing fluid pulses 104i-o sub-stage 108, 110,
112, and 114 is described by a pulse cycle duration t.sub.pcycle.
The pulse cycle duration t.sub.pcycle includes a
proppant-containing fluid pulse duration t.sub.pcp and a
proppant-free fluid pulse duration t.sub.pfp, where the durations
t.sub.pcycle, t.sub.pcp, and t.sub.pfp may be the same or different
for each sub-stage 108, 110, 112, and 114 and the durations
t.sub.pcp and t.sub.pfp in each cycle may be the same or
different.
[0276] Referring now to FIG. 1D, another embodiment of a fracturing
pulse or slug sequence, generally 160, is shown to include a pad
stage 162 having a pad duration t.sub.pad, a proppant placement
stage 164 having a proppant placement duration t.sub.pp, and a
tail-in stage 166 having a tail-in duration t.sub.t. The proppant
placement stage 164 is shown here as a continuous increasing volume
ramp. The ramp 164 includes a continuous increasing
proppant-containing fluid injection 164a and a plurality of an
aggregating composition or an aggregating composition and a coating
crosslinking composition pulses 164b-h. Each of the pulses 164b-h
may be of the same or different duration.
[0277] Referring now to FIG. 2A, an embodiment ofa proppant pattern
established in a formation penetrated by a well bore by a proppant
placement stage, generally 200, is shown to include a well bore 202
penetrating a formation 204. The well bore 202 includes a cemented
or uncemented casing string 206 and a broad fracture 208 formed in
the formation 204 through a plurality of perforations 210 in the
string 206 by a viscosified pad fluid injected into the formation
204 at a sufficient pressure to form the fracture 208. The fracture
208 includes a proppant pattern 212 formed by the proppant
placement stage 200 including a plurality of proppant-free fluid
pulses 214a-h and an alternating plurality of proppant-containing
fluid pulses 216a-g. The proppant pattern 212 comprises a set of
proppant networks 218a-g including proppant pillars 220a-g and flow
pathways 222a-g. The proppant-containing fluid pulses 216a-g have
the same or different proppant compositions (shown here as
different) giving rise to the same or different proppant pillars
218a-g (shown here as different), where the proppant-containing
fluid pulse proppant compositions differ in at least one proppant
composition property including proppant type, proppant size,
proppant shape, and concentrations of each proppant type, size,
shape, or mixtures thereof and mixtures or combinations
thereof.
[0278] Referring now to FIG. 2B, an embodiment ofa proppant pattern
established in a formation penetrated by a well bore by a proppant
placement stage, generally 200, is shown to include a well bore 202
penetrating a formation 204. The well bore 202 includes a cemented
or uncemented casing string 206 and a narrow fracture 208 formed in
the formation 204 through a plurality of perforations 210 in the
string 206 by a viscosified pad fluid injected into the formation
204 at a sufficient pressure to form the fracture 208. The fracture
208 includes a proppant pattern 212 formed by the proppant
placement stage 200 including a plurality of proppant-free fluid
pulses 214a-g and an alternating plurality of proppant-containing
fluid pulses 216a-f. The proppant pattern 212 comprises a set of
proppant networks 218a-f including proppant pillars 220a-f and flow
pathways 222a-f. The proppant-containing fluid pulses 216a-f have
the same or different proppant compositions (shown here as
different) giving rise to the same or different proppant pillars
220a-f (shown here as different), where the proppant-containing
fluid pulse proppant compositions differ in at least one proppant
composition property including proppant type, proppant size,
proppant shape, and concentrations of each proppant type, size,
shape, or mixtures thereof and mixtures or combinations
thereof.
[0279] Referring now to FIG. 2C, an embodiment ofa proppant pattern
established in a formation penetrated by a well bore by a proppant
placement stage, generally 200, is shown to include a well bore 202
penetrating a formation 204. The well bore 202 includes a cemented
or uncemented casing string 206 and an illustrative square fracture
208 formed in the formation 204 through a plurality of perforations
210 in the string 206 by a viscosified pad fluid injected into the
formation 204 at a sufficient pressure to form the fracture 208.
The fracture 208 includes a proppant pattern 212 formed by the
proppant placement stage 200 including a plurality of proppant-free
fluid pulses 214a-e and an alternating plurality of
proppant-containing fluid pulses 216a-f. The proppant pattern 212
comprises a set of proppant networks 218a-f including proppant
pillar groups 220a-f and major flow pathways 222a-f and minor flow
pathways within pillar groups (not shown, but evident from the
groups). The proppant-containing fluid pulses 216a-f have the same
or different proppant compositions (shown here as different) giving
rise to the same or different proppant pillars 220a-f (shown here
as different), where the proppant-containing fluid pulse proppant
compositions differ in at least one proppant composition property
including proppant type, proppant size, proppant shape, and
concentrations of each proppant type, size, shape, or mixtures
thereof and mixtures or combinations thereof.
[0280] Referring now to FIG. 2D, an embodiment of a proppant
pattern established in a formation penetrated by a well bore by a
proppant placement stage, generally 200, is shown to include a well
bore 202 penetrating a formation 204. The well bore 202 includes a
cemented or uncemented casing string 206 and a highly branched
fracture 208 formed in the formation 204 through perforations 210
in the string 206 by a viscosified pad fluid injected into the
formation 204 at a sufficient pressure to form the fracture 208.
The fracture 208 includes a proppant pattern 212 formed by the
proppant placement stage 200 including a plurality of proppant-free
fluid pulses 214 and an alternating plurality of
proppant-containing fluid pulses 216. The proppant pattern 212
comprises proppant pillars 218 and flow pathways within pillar
groups (not shown). The proppant-containing fluid pulses 216 may
have the same or different proppant compositions (shown here as
different) giving rise to the same or different proppant pillars
218 (shown here as different), where the proppant-containing fluid
pulse proppant compositions differ in at least one proppant
composition property including proppant type, proppant size,
proppant shape, and concentrations of each proppant type, size,
shape, or mixtures thereof and mixtures or combinations
thereof.
[0281] Referring now to FIG. 2E, an embodiment of a frac pack
pattern established in a formation penetrated by a well bore,
generally 200, is shown to include a well bore 202 penetrating a
formation 204. The well bore 202 includes a cemented or uncemented
casing string 206 and a frac pack 208 formed in the formation 204
through a plurality of perforations 210 in the string 206 by a
viscosified proppant-containing fluid injected into the formation
204 at a sufficient pressure to form the frac pack 208. The frac
pack 208 includes a proppant pillar pattern 212 including a
plurality of proppant pillars 214 and a plurality of flow pathways
216 therethrough.
[0282] Referring now to FIGS. 3A-I, nine different pillar
configurations are illustrated, each configuration including
different proppant types in different arrangements. Looking at FIG.
3A, a regular proppant configuration 300 is shown to include
treated solid proppant particles 302 having an aggregating
composition coating 304 thereon. Looking at FIG. 3B, an irregular
proppant configuration 306 is shown to include treated solid
proppant particles 308 having an aggregating composition coating
310 thereon, crosslink treated solid proppant particles 312 having
a crosslinked aggregating composition coating 314 thereon and
hollow untreated proppant particles 316. Looking at FIG. 3C, an
irregular proppant configuration 318 is shown to include crosslink
treated solid proppant particles 320 having a crosslinked
aggregating composition coating 322 thereon and untreated solid
proppant particles 324. Looking at FIG. 3D, an irregular proppant
configuration 326 is shown to include two different sized treated
solid proppant particles 328 and 330 having aggregating composition
coatings 332 and 334 thereon. Looking at FIG. 3E, an irregular
proppant configuration 336 is shown to include treated hollow
proppant particles 338 having an aggregating composition coating
340 thereon, crosslink treated hollow proppant particles 342 having
a crosslinked aggregating composition coating 344 thereon, treated
irregular solid proppant particles 346 having an aggregating
composition coating 348 thereon, crosslinked treated irregular
solid proppant particles 350 having a crosslinked aggregating
composition coating 352 thereon, and solid untreated proppant
particles 354. Looking at FIG. 3F, an irregular proppant
configuration 356 is shown to include treated solid proppant
particles 358 having an aggregating composition coating 360 thereon
and hollow untreated proppant particles 362. Looking at FIG. 3G,
another regular proppant configuration 364 is shown to include
treated solid regular proppant particles 366 having an aggregating
composition coating 368 thereon and a non-erodible fibers 370
entangled with and partially surrounding the cluster. Looking at
FIG. 3H, another irregular proppant configuration 372 is shown to
include treated solid regular proppant particles 374 having an
aggregating composition coating 376 thereon, crosslink treated
solid regular proppant particles 378 having an aggregating
composition coating 380 thereon, untreated solid regular proppant
particles 382, and an entangled non-erodible fiber 384. Looking at
FIG. 3I, another irregular proppant configuration 386 is shown to
include treated solid regular proppant particles 388 having an
aggregating composition coating 390 thereon, untreated solid
regular proppant particles 392, and surrounding two different
non-erodible fibers 394 and 396. Of course, it should be recognized
that any given fracturing application may include any of this
proppant groups in any relative proportions.
[0283] Referring now to FIGS. 4A-J, ten different pillar groups are
illustrated, each group including four pillars, each figure having
a different proppant pillar type differing in proppant particle
type and pillar configuration. Looking at FIG. 4A, a pillar group
configuration 400 is shown to include four irregular proppant
pillars 402 including treated solid regular proppant particles 404
and untreated regular proppant particles 406. Looking at FIG. 4B,
another pillar group configuration 408 is shown to include four
regular proppant pillars 410 including treated solid regular
proppant particles 412. Looking at FIG. 4C, a pillar group
configuration 414 is shown to include four irregular proppant
pillars 416 including treated solid regular proppant particles 418,
crosslink treated solid regular proppant particles 420, and
untreated hollow regular proppant particles 422. Looking at FIG.
4D, a pillar group configuration 424 is shown to include four
irregular proppant pillars 426 including treated solid regular
proppant particles 428, crosslink treated solid regular proppant
particles 430, treated solid irregular proppant particle 432,
crosslink treated solid irregular proppant particle 434, and
untreated regular proppant particles 436. Looking at FIG. 4E, a
pillar group configuration 438 is shown to include four irregular
proppant pillars 440 including two different sized treated solid
proppant particles 442 and 444. Looking at FIG. 4F, a pillar group
configuration 446 is shown to include four irregular proppant
pillars 448 including crosslink treated hollow regular proppant
particles 450 and untreated solid regular proppant particles 452.
Looking at FIG. 4G, a pillar group configuration 454 is shown to
include six different proppant pillar types 456a-f including
different treated, crosslink treated, and untreated proppant
particles. Looking at FIG. 4H, a pillar group configuration 458 is
shown to include two irregular proppant pillar types 460a&b
including different treated, crosslink treated, and untreated
proppant particles. Looking at FIG. 4I, a pillar group
configuration 462 is shown to include two irregular proppant pillar
types 464a&b including different treated and untreated proppant
particles. Looking at FIG. 4J, a pillar group configuration 466 is
shown to include six regular and irregular proppant pillar types
468a-f including different treated, crosslink treated, and
untreated proppant particles.
[0284] Referring now to FIGS. 5A-D, four perforation patterns are
illustrated, each pattern including different perforation groups
separated by non-perforation spans. Looking at FIG. 5A, a
perforation interval 500 is shown in a well bore 502 that my be
cased with a cemented or non-cemented casing 504. The interval 500
includes two perforation groups 506 and 508. The perforation group
506 comprises six tightly spaced perforations 510, while the second
group 508 includes a single perforation 512. Looking at FIG. 5B, a
perforation interval 520 is shown in a well bore 522 that my be
cased with a cemented or non-cemented casing 524. The interval 520
includes two perforation groups 526 and 528. The perforation group
526 comprises six tightly spaced perforations 530, while the second
group 528 includes three tightly spaced perforations 532. Looking
at FIG. 5C, a perforation interval 540 is shown in a well bore 542
that my be cased with a cemented or non-cemented casing 544. The
interval 540 includes three perforation groups 546, 548, and 550.
The perforation group 546 comprises five tightly spaced
perforations 552; the second group 548 includes three tightly
perforations 554; and the third perforation group 550 includes
three tightly perforations 556. Looking at FIG. 5D, a perforation
interval 560 is shown in a well bore 562 that my be cased with a
cemented or non-cemented casing 564. The interval 560 includes
three perforation groups 566, 568, and 570. The perforation group
566 comprises four less tightly spaced perforations 572; the second
group 568 includes three tightly perforations 574; and the third
perforation group 570 includes six tightly spaced perforations 576.
It should be recognized that the above perforation intervals are
simply included as illustrations of different perforation
configuration. These intervals may be repeated in blocks in
patterns to produce long or short perforation configurations.
Additionally, it should be recognized that dimensions of the
perforation may be adjusted so that each group of perforation will
selectively permit different proppant particles sizes
therethrough.
EXPERIMENTS OF THE INVENTION
Example 1
[0285] Referring now to FIG. 6, a table is shown that provides zeta
potential ranges and corresponding aggregating propensities.
Maximal aggregating potential or propensity is associated with zeta
potentials between +3 mV and -5 mV; strong aggregating potential or
propensity is associated with zeta potentials between -5 mV and -10
mV; medium to weak aggregating potential or propensity is
associated with zeta potentials between -10 mV and -15 mV; a
threshold aggregating potential or propensity is associated with
zeta potentials between -16 mV and -30 mV; and low or little
aggregating potential or propensity is associated with zeta
potentials between -31 mV and -100 mV or lower.
[0286] FIG. 6 also includes experimental data of untreated silica
and silica treated with the aggregating agent SandAid.TM., an
amine-phosphate reaction product type aggregating agent available
from Weatherford International, which forms a partial or complete
coating on the silica altering the aggregating propensity of the
treated silica. In fact, untreated silica have a zeta potential of
about -47.85 mV, while the SandAid.TM. treated silica has a zeta
potential of about -1.58 mV, thus, changing a non-aggregating
proppant into a maximally aggregating proppant. Similarly,
untreated coal which as a zeta potential of about -28.37 mV, a
threshold aggregating proppant, when treated with SandAid.TM., the
untreated coal is converted into a treated coal proppant having a
zeta potential of about 1.194 mV, converting the threshold
aggregating proppant into a maximally aggregating proppant. By
changing the relative amounts of treated and untreated silica or
coal, one may readily adjust the bulk or relative zeta potential of
a proppant composition for used in the proppant-containing
fracturing fluids of this invention.
Example 2
[0287] This example illustrates the agglomeration of sand with
SandAid and then consolidation with a ZnCl.sub.2 solution.
[0288] 1.75 mL of SandAid.TM. (7 wt % w.r.t sand weight) was added
to 25 mL of a 2 wt. % aqueous KCl solution containing 25 g of 200
mesh sand as shown in FIG. 7A. After stirring with a mechanical
stirrer at 450 rpm for 1 minute, the sand clustered and turned
brown in color due to the SandAid coating. The supernatant was
decanted off to produce a first SandAid.TM. treatment. Add another
25 mL of a 2 wt. % aqueous KCl solution to the sand clusters and
proceed to the second and third SandAid treatments. Later on, 25 mL
of a 2 wt. % aqueous KCl solution was used to wash the
SandAid.TM.-coated sand in order to remove unreacted materials. The
agglomerated sand looked like a soft touching, clay-like material
as shown in FIG. 7B. To consolidate the texture of the agglomerated
sand produced by the first treatment, 25 mL of a 2 wt. % aqueous
ZnCl.sub.2 solution was subsequently added. The mixture was further
mixed with a mechanical stirrer at 450 rpm for 1 min, followed by
decanting the supernatant. The agglomerated material formed
strengthened agglomerated particles and is no longer soft to touch
or clay-like and has the appearance shown in FIG. 7C.
[0289] SandAid-coated 100 mesh sand was transferred to a 4 oz jar
and topped with water as shown in FIG. 8A. Same amount of
SandAid.TM.-coated 200 mesh sand, after 2 wt. % ZnCl.sub.2
treatment, was also transferred to another glass jar as shown in
FIG. 8B. Both of them showed perfect sand clusters at room
temperature. The two bottles were heated at 180.degree. F. in water
bath for 1 hour, the sand cluster before ZnCl.sub.2 treatment
became less agglomerated. It no longer kept its entire chunk but
started to fall apart in a flipped jar as shown in FIG. 8C.
However, the sand cluster with ZnCl.sub.2 treatment was able to
sustain such a harsh condition without losing its original
agglomeration FIG. 8D. It indicates that ZnCl.sub.2 can consolidate
SandAid.TM.-coated proppants, enhancing not only the texture
hardness but also the thermal stability of the agglomerated
proppant packs.
High Temperature and Pressure Testing of Crosslinked and
Non-Crosslinked Coated Proppant
[0290] Carbolite ceramic proppant mainly composed of
Al.sub.2O.sub.3 and SiO.sub.2, was dispersed in water, followed by
treated with 7 wt. % of SandAid and then washed with a 2 wt. %
aqueous KCl solution for three times. The agglomerated proppant was
subsequently transferred to a 4 oz glass jar and topped with water
as shown FIG. 9A. In another experiment treated CARBOLITE.RTM.
proppant (registered trademark of CARBO Ceramics) is blended with
the same amount of SandAid.TM. and washed three times with 2 wt. %
KCl. 2 wt. % aqueous ZnCl.sub.2 was used to crosslink the
SandAid.TM.-coated CarboLite proppant right after the third KCl
wash step as shown in FIG. 9C. Both samples showed good
agglomeration at room temperature. To test their agglomeration
properties at high temperature and high pressure (HTHP) conditions,
the jar in FIG. 9A and FIG. 9C without lid were transferred into a
pressurized cell which is charged to 300 psi at room temperature to
prevent solutions from evaporation. The cells were placed in a
137.degree. C. oven for 7 days at a pressure of 240 psi, both
proppant packs still kept their original good agglomeration without
falling apart. Interestingly, the proppant with ZnCl.sub.2
treatment as shown in FIG. 9D showed higher amount of SandAid
remained on its surface than the one without the treatment as shown
in FIG. 9B. This could be explained that ZnCl.sub.2 played an
important role to crosslink the SandAid.TM. on proppant surface
which prevent the SandAid.TM. desorbing from proppant and further
enhance the texture hardness of the agglomerated proppants,
Maximum Sand Free Rate Test (MSFRT) on the SandAid.TM.-Coated Sand
with the Assistance of ZnCl.sub.2
[0291] Two experiments were run with 200 mesh sand (100 g) in the
maximum sand free rate test (MSFRT) apparatus at 180.degree. F. In
one experiment the sand pack was treated with 7 wt. % SandAid.TM.
whereas in other case it was treated with 7 wt. % SandAid.TM.
followed by post-flush with 100 ml of a 2 wt. % aqueous ZnCl.sub.2
solution. The MSFRT was carried out at 180.degree. F. to measure
the maximum flow rate where the agglomerated sand would not fall
apart and produce sand. In other words, the higher the value for
the maximum sand free rate is, the more consolidated the tested
sand pack would be. The MSFRT for the SandAid.TM.-coated sand
started producing sand at a flow rate of <10 mL/min at
180.degree. F., whereas the value for the SandAid.TM.-coated sand
crosslinked by ZnCl.sub.2 could approach .about.200 mL/min (system
limitation) under the same condition without sand production. FIG.
10 shows the agglomerated sand pack after the MSFRT. The dark brown
region (bottom part) indicated the sand after SandAid.TM. coating
and ZnCl.sub.2 crosslinking. It touched as hard as cement.
Regain Brine Permeability to 5% Sandaid with and Without ZnCl.sub.2
Flush
[0292] The regain permeability tests were conducted to show whether
or not the ZnCl.sub.2 flush would have any adverse effect upon the
regain brine permeability. When the percent brine regain values are
compared, 69.3% (without ZnCl.sub.2) and 75.6% (with ZnCl.sub.2),
it appears that the addition of the ZnCl.sub.2 does not cause more
damage. Table 1 tabulates a regain permeability results.
TABLE-US-00003 TABLE 1 Regain Brine Permeability to 5% Sand Aid
with and without ZnCl.sub.2 Flush Initial Pre- Sand Aid Over-
Shut-in Final Permeability Flush Injection Flush Permeability
Specific Kleen Kleen Sand Kleen Regain ID KCl Kw Rinse KCl Rinse
Aid Rinse ZnCl.sub.2 Time Kw % Regain 1 2.0% 107 0.30% 2.0% 0.30%
5% 0.30% -- 6 hr 74.1 69.3% 2 2.0% 95.9 0.30% 2.0% 0.30% 5% 0.30%
2% 6 hr 72.5 75.6%
[0293] FIGS. 11A&B show agglomerated sand packs after the
regain permeability tests. Looking at FIG. 11A, SandAid treated
sand was tested at 180.degree. F. with a 200 psi back pressure and
a net confining stress of 1200 psi. A regain brine permeability was
measured in the production direction and found to be 74.1 md. A
percent regain brine permeability of 69.3% was calculated. Looking
at FIG. 11B, crosslinked SandAid treated was treated under the same
testing conditions (i.e., SandAid-treated sand with 2% ZnCl.sub.2
flush) was found to have a regain brine permeability of 72.5 md and
75.6% of regain brine permeability.
[0294] 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.
* * * * *