U.S. patent application number 13/748069 was filed with the patent office on 2013-05-30 for aqueous gels for well bore strengthening.
This patent application is currently assigned to M-I L.L.C.. The applicant listed for this patent is M-I L.L.C.. Invention is credited to David Ballard.
Application Number | 20130133888 13/748069 |
Document ID | / |
Family ID | 38620177 |
Filed Date | 2013-05-30 |
United States Patent
Application |
20130133888 |
Kind Code |
A1 |
Ballard; David |
May 30, 2013 |
AQUEOUS GELS FOR WELL BORE STRENGTHENING
Abstract
A process for treating an earth formation is provided, the
process may include: injecting a gelling agent into the earthen
formation; injecting a crosslinking agent into the earthen
formation; and reacting the gelling agent and the crosslinking
agent to form a gel. The gelling agent may include at least one of
a lignin, a lignosulfonate, a tannin, a tannic acid, a modified
lignin, a modified lignosulfonate, a modified tannin, a modified
tannic acid, biopolymers, polyacrylates, polyacrylamides, polyether
amines, poly vinyl amines, and combinations thereof The
crosslinking agent may include at least one of ethylene glycol
diglycidyl ether, propylene glycol diglycidyl ether, butylene
glycol diglycidyl ether, sorbitol polyglycidyl ether,
trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether,
diglycidyl ether of neopentyl glycol, epoxidized 1,6-hexanediol,
aziridine derivatives, epoxy functionalized polyalkalene glycols,
an oxidized starch, and combinations thereof.
Inventors: |
Ballard; David;
(Aberdeenshire, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
M-I L.L.C.; |
Houston |
TX |
US |
|
|
Assignee: |
M-I L.L.C.
Houston
TX
|
Family ID: |
38620177 |
Appl. No.: |
13/748069 |
Filed: |
January 23, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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11737612 |
Apr 19, 2007 |
8377853 |
|
|
13748069 |
|
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60793407 |
Apr 20, 2006 |
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Current U.S.
Class: |
166/292 ;
507/108 |
Current CPC
Class: |
C09K 17/32 20130101;
C09K 8/08 20130101; C09K 8/512 20130101; C09K 8/588 20130101; C09K
8/203 20130101; E21B 33/13 20130101 |
Class at
Publication: |
166/292 ;
507/108 |
International
Class: |
C09K 8/08 20060101
C09K008/08; E21B 33/13 20060101 E21B033/13 |
Claims
1. (canceled)
2. (canceled)
3. (canceled)
4. (canceled)
5. (canceled)
6. (canceled)
7. A gel comprising: the reaction product of a gelling agent and a
crosslinking agent; wherein the gelling agent comprises at least
one of a lignin, a lignosulfonate, a tannin, a tannic acid, a
modified lignin, a modified lignosulfonate, a modified tannin, a
modified tannic acid, polyacrylates, polyacrylamides, polyether
amines, poly vinyl amines, and combinations thereof; and wherein
the crosslinking agent comprises at least one of ethylene glycol
diglycidyl ether, propylene glycol diglycidyl ether, butylene
glycol diglycidyl ether, trimethylolpropane triglycidyl ether,
sorbitol polyglyleidyl ether, diglycidyl ether of neopentyl glycol,
epoxidized 1,6-hexanediol, aziridine derivatives,
trimethylolpropane, tris)beta-ethyleniminopropionate), eopxy
functionalized polyalkalene glycols, and combinations thereof; and
wherein the weight percent of the gelling agent relative to the
total weight of the gel ranges from 11 to 25 weight percent.
8. The gel of claim 7, wherein the reaction product is formed at a
temperature between 25.degree. C. and 350.degree. C.
9. The gel of claim 7, wherein the gel has a hardness of 300
gram-force or greater at a penetration depth of 20 mm.
10. The gel of claim 7, wherein the gel has a hardness of 1000
gram-force or greater at a penetration depth of 20 mm.
11. The gel of claim 7, wherein the gel has a hardness of 3,000
gram-force or greater at a penetration depth of 20 mm.
12. The gel of claim 7, wherein the gel has a hardness of 5,000
gram-force or greater at a penetration depth of 25 mm.
13. The gel of claim 7, wherein the gel has an initial viscosity in
the range of approximately 500 centipoise to 20,000 centipoise
measured at 20.degree. C. using an LV2 spindle at low rotational
speeds.
14. The gel of claim 7, wherein the gel has an initial viscosity in
the range of approximately 1000 centipoise to 5,000 centipoise
measured at 20.degree. C. using an LV2 spindle at low rotational
speeds.
15. The gel of claim 7, wherein the weight percent of the gelling
agent relative to the total weight of the gel may range from 8 to
25 weight percent.
16. The gel of claim 7, wherein the weight percent of the gelling
agent relative to the total weight of the gel may range from 10 to
20 weight percent.
17. The gel of claim 7, wherein the weight percent of the gelling
agent relative to the total weight of the gel may range from 11 to
17 weight percent.
18. Use of the gel of claim 7 in a drilling fluid, in a loss
circulation material pill, as a soil stabilizing agent, as a dust
suppressant, or as a heat transfer fluid loss additive.
19. A method of treating an earth formation comprising: injecting
an aqueous gel comprising at least one gelling agent and at least
one crosslinking agent in an aqueous solution and having an initial
viscosity in the range of approximately 500 centipoise to 100,000
centipoise measured at 20.degree. C. using an LV2 spindle at low
rotational speeds, wherein the combined weight percent of the
gelling agents and crosslinking agents relative to the total weight
of water in the solution may range from 5 to 100 weight percent;
and allowing the aqueous gel to react in the earth formation,
20. The method of claim 19, further comprising preparing the
aqueous gel.
21. The method of claim 19, wherein the combined weight percent of
the gelling agents and crosslinking agents relative to the total
weight of water in the solution may range from 5 to 100 weight
percent.
22. The method of claim 19, wherein the combined weight percent of
the gelling agents and crosslinking agents relative to the total
weight of water in the solution may range from 20 to 70 weight
percent.
23. The method of claim 19, wherein the combined weight percent of
the gelling agents and crosslinking agents relative to the total
weight of water in the solution may range from 25 to 65 weight
percent.
24. The method of claim 19, wherein the gelling agent comprises at
least one of a lignin, a lignosulfonate, a tannin, a tannic acid, a
modified lignin, a modified lignosulfonate, a modified tannin, a
modified tannic acid, polyacrylates, polyacrylamides, polyether
amines, poly vinyl amines, polyethylene imines, and combinations
thereof.
25. The method of claim 19, wherein the crosslinking agent
comprises at least of ethylene glycol diglycidyl ether, propylene
glycol diglycidyl ether, butylene glycol diglycidyl ether,
trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether,
diglycidyl ether of neopentyl glycol, epoxidized 1,6-hexanediol,
aziridine derivatives, trimethylolpropane
tris(beta-ethyleniminopropionate), epoxy functionalized
polyalkalene glycols, an and combinations thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to U.S. Provisional Patent
Application No. 60/793,407, filed Apr. 20, 2006, the disclosure of
which is incorporated herein by reference.
BACKGROUND OF INVENTION
[0002] 1. Field of the Invention
[0003] Embodiments disclosed herein relate generally to lignin,
lignosulfonate, tannin, and tannic acid gels. In some embodiments,
the gels are formed by reacting a low- or non-toxic crosslinking
agent with lignin, lignosulfonate, or other gelling agents.
[0004] 2. Background
[0005] Lost circulation is a recurring drilling problem,
characterized by loss of drilling mud into downhole formations that
are fractured, highly permeable, porous, cavernous, or vugular.
These earth formations can include shale, sands, gravel, shell
beds, reef deposits, limestone, dolomite, and chalk, among others.
Other problems encountered while drilling and producing oil and gas
include stuck pipe, hole collapse, loss of well control, and loss
of or decreased production. In attempting to cure these and other
problems, crosslinkable or absorbing polymers, loss control
material (LCM) pills, and cement squeezes have been employed, each
of which may include materials such as lignins and lignosulfonates,
as well as lignin and lignosulfonate gels.
[0006] Lignin is a by-product of the sulfite process of making
paper, and when combined with sodium dichromate, forms an insoluble
gel after a short time. Lignin-based grouts or gels can be used in
porous earth formations for decreasing the flow of water through
the formation, or for increasing the load-bearing capacity of the
formation. Lignin grouts have also been used effectively in sealing
fine fissures in fractured rock or concrete.
[0007] In addition to sodium bichromate, other crosslinking agents
used in forming lignin-based gels include potassium bichromate,
ferric chloride, sulfuric acid, aluminum sulfate(alum), aluminum
chloride, ammonium persulfate, and copper sulfate. The bichromates
have been the most widely used and are the most satisfactory, as
they return a gel having a desired strength.
[0008] Lignosulfonate gels have also been used in gel treatments,
such as to reduce channeling of solvent and water through drilling
formations. In particular, chrome-lignosulfonate time-set gels have
been found to be successful in forming an in-situ time-set gel. For
example, see Wagner et al., "Field application of lignosulfonate
gels to reduce channeling. South Swan Hills Miscible Unit, Alberta,
Canada," SPE 15547, 1986.
[0009] U.S. Pat. Nos. 3,672,817 and 4,001,205 disclose processes
for producing a dispersant by reacting a water-soluble sulfonated
lignin and epichlorohydrin. U.S. Pat. No. 4,168,371 discloses a
process for making lignin-based gels by reacting a water-insoluble
lignin and epichlorohydrin, where the reaction is catalyzed by an
alkali metal hydroxide. U.S. Pat. No. 4,244,728 discloses a process
for producing a crosslinked lignin gel which is the reaction
product of an aqueous solution of alkali lignin with a crosslinking
agent such as formaldehyde, glyoxal, or glutaric dialdehyde.
[0010] Lignin and lignosulfonate gels formed with bichromates,
epichlorohydrin, and aldehydes, however, are no longer
environmentally acceptable due to the toxicity of the chromium,
aldehyde, and epichlorohydrin crosslinking agents. Unfortunately,
other reactants may not result in a gel of equivalent strength as
when these crosslinking agents are used. For example, lignin gels
formed from ammonium persulfate generally have a strength
approximately 40 percent of that of a similar grout mixture in
which bichromate is used as a reactant.
[0011] Accordingly, there exists a need for lignin-based and
lignosulfonate-based gels formed from less toxic or non-toxic
crosslinking agents, and for gels that have equivalent or greater
strength than those formed from epichlorohydrins, bichromates or
other chromium catalysts, and other toxic crosslinking agents.
SUMMARY OF INVENTION
[0012] In one aspect, embodiments disclosed herein relate to a
process for stengthening a wellbore. The process may include:
injecting a gelling agent into the earthen formation; injecting a
crosslinking agent into the earthen formation; and reacting the
gelling agent and the crosslinking agent to form a gel. The gelling
agent may include at least one of a lignin, a lignosulfonate, a
tannin, a tannic acid, a modified lignin, a modified
lignosulfonate, a modified tannin, a modified tannic acid,
biopolymers, starches, carboxy methyl cellulose, polyacrylates,
polyacrylamides, polyamines, polyether amines, poly vinyl amines,
polyethylene imines, and combinations thereof. The crosslinking
agent may include at least one of ethylene glycol diglycidyl ether,
propylene glycol diglycidyl ether, butylene glycol diglycidyl
ether, trimethylolpropane triglycidyl ether, sorbitol polyglycidyl
ether, diglycidyl ether of neopentyl glycol, epoxidized
1,6-hexanediol, aziridine derivatives, epoxy functionalized
polyalkalene glycols, an oxidized starch, also known as polymeric
dialdehyde, an aldehyde adduct, a tetra methoxy propane, a
hydrolized acetal, and combinations thereof.
[0013] In another aspect, embodiments disclosed herein relate to a
gel formed from a crosslinking agent and a gelling agent. The
gelling agent may include at least one of a lignin, a
lignosulfonate, a tannin, a tannic acid, a modified lignin, a
modified lignosulfonate, a modified tannin, a modified tannic acid,
biopolymers, starches, carboxy methyl cellulose, polyacrylates,
polyacrylamides, polyamines, polyether amines, poly vinyl amines,
polyethylene imines, and combinations thereof. The crosslinking
agent may include at least one of ethylene glycol diglycidyl ether,
propylene glycol diglycidyl ether, trimethylolpropane triglycidyl
ether, diglycidyl ether of neopentyl glycol, epoxidized
1,6-hexanediol, butylene glycol diglycidyl ether, aziridine
derivatives, epoxy functionalized polyalkalene glycols, an oxidized
starch, also known as polymeric dialdehyde, an aldehyde adduct, a
tetra methoxy propane, a hydrolized acetal, and combinations
thereof.
[0014] In another aspect, embodiments disclosed herein relate to a
method of treating an earth formation. The method may include
injecting an aqueous gel into an earth formation, the aqueous gel
comprising at least one gelling agent and at least one crosslinking
agent dissolved in an aqueous solution and having an initial
viscosity in the range of approximately 500 centipoise to 100,000
centipoise measured at 20.degree. C. using an RV2 spindle at low
rotational speeds (12 rpm or less), and allowing the aqueous gel to
react in the earth formation.
[0015] Other aspects and advantages of the invention will be
apparent from the following description and the appended
claims.
DETAILED DESCRIPTION
[0016] In one aspect, embodiments disclosed herein relate to gels
formed from lignins, lignosulfonates, tannins, tannic acid, and
other gelling agents. In other aspects, embodiments disclosed
herein relate to processes for making gels, and applications in
which the gels disclosed herein may be useful.
[0017] A crosslinking agent and a gelling agent (the material to be
crosslinked) may be reacted to form a gel. In some embodiments, the
gelling agent may be dissolved in water to form a solution, and a
crosslinking agent may be added to the solution, reacting with the
gelling agent to form a gel. In other embodiments, the pH of the
solution may be adjusted to effect or enhance gel formation.
[0018] Gelling Agents/Materials to be Crosslinked
[0019] In some embodiments, gelling agents, or the materials to be
crosslinked, may include lignins, lignosulfonates, tannins, tannic
acids, and combinations thereof. In other embodiments, materials to
be crosslinked may include modified lignins, modified
lignosulfonates, modified tannins, modified tannic acids, and
combinations thereof. In certain embodiments, tannins may be
modified to have a higher phenol content. In certain other
embodiments, tannins may be treated with amines.
[0020] In other embodiments, gelling agents may include
biopolymers, starches, carboxy methyl cellulose, polyacrylates,
polyacrylamides, and combinations thereof. In other embodiments,
gelling agents may include polyamines such as diethylene triamine
and triethylene tetramine, and the like. In yet other embodiments,
gelling agents may include polyether amines, poly vinyl amines and
polyethylene imines.
[0021] In some embodiments, starches may include natural starches,
chemically modified starches, and mixtures of one or more natural
and/or chemically modified starches. Natural starches may include
those of potato, wheat, tapioca, rice, corn, and roots having a
high starch content, among others. Chemically modified starches may
include carboxymethyl starch, hydroxyethyl starch, hydroxypropyl
starch, acetate starch, sulfamate starch, phosphate starch, and
nitrogen modified starch, among others.
[0022] In yet other embodiments, combinations of any of the above
listed materials to be crosslinked may be used.
[0023] Cross-Linking Agents
[0024] The desired gel may be achieved by reacting the above
gelling agents and a crosslinking agent. In some embodiments, the
crosslinking agent may include ethylene glycol diglycidyl ether,
propylene glycol diglycidyl ether, butylene glycol diglycidyl
ether, sorbitol polyglycidyl ether, aziridine derivatives, epoxy
functionalized polyalkalene glycols, an oxidized starch (polymeric
dialdehyde), and combinations thereof.
[0025] In other embodiments, the crosslinking agent may include an
acetal that can be hydrolized to produce the aldehyde in situ. For
example, the crosslinking agent may include an aldehyde adduct, a
tetra methoxy propane, or the bisulphite addition compounds of the
aldehydes. For example, a formaldehyde adduct may be formed by
reacting formaldehyde and a compound selected from sulfurous acid
and its water soluble salts, such as the alkali metal salts (e.g.,
sodium or potassium salts). In one embodiment, the salt used may be
sodium bisulfite. In addition to using the alkali metal salts,
ammonium and tertiary amine salts of sulfurous acid such as
ammonium bisulfite or trimethylamine sulfite may be used to form an
adduct.
[0026] In other embodiments, the crosslinking agent may be a
diepoxide or a triepoxide. In yet other embodiments, the
crosslinking agent may include trimethylolpropane triglycidyl
ether, diglycidyl ether of neopentyl glycol, epoxidized
1,6-hexanediol, 1,4-butanediol diglycidyl ether (BDDGE),
1,2,7,8-diepoxyoctane,
3-(bis(glycidoxymethyl)-methoxy)-1,2-propanediol,
1,4-cyclohexanedimethanol diglycidyl ether, 4-vinyl-1-cyclohexene
diepoxide, 1,2,5,6-diepoxycyclooctane, and bisphenol A diglycidyl
ether, or combinations thereof.
[0027] Gel Preparation
[0028] In one embodiment, the gel is formed by combining a gelling
agent and a crosslinking agent in an aqueous solution. Aqueous
solutions that may be appropriate include water-based muds for use
in downhole applications and may include fresh water, sea water,
brine, mixture of water and water soluble organic compounds, and
mixtures thereof.
[0029] The crosslinking agent may be present in an amount effective
to crosslink the gelling agent. In some embodiments, the
crosslinking agent may be used in an amount ranging from about 0.05
to about 50 weight percent based on the total weight of the gelling
agent(s). In other embodiments, the crosslinking agent may be used
in an amount ranging from about 5 to about 40 weight percent based
on the total weight of the gelling agent(s); from about 10 to about
35 weight percent in yet other embodiments. In other embodiments, a
weight ratio of the crosslinking agent to the gelling agent may be
from 1:2000 to 1:1; from 1:20 to 1:2 in other embodiments, and from
1:10 to about 1:3 in yet other embodiments.
[0030] The amount of crosslinking agent may affect the hardness of
the resulting gel. For example, in some embodiments, for a constant
weight of gelling agent, increasing the amount of crosslinking
agent may result in a higher crosslink density, and therefore a
harder gel. Using the guidelines provided herein, those skilled in
the art will be capable of determining a suitable amount of
cross-linking agent to employ to achieve a gel of the desired
hardness.
[0031] Aging Temperature
[0032] In some embodiments, the gelling agent and the crosslinking
agent may be reacted at a temperature from -50 to 300.degree. C. In
other embodiments, the gelling agent and the crosslinking agent may
be reacted at a temperature from 25 to 250.degree. C.; from 50 to
150.degree. C. in other embodiments; and from 60 to 100.degree. C.
in yet other embodiments. In certain embodiments, the reaction
temperature determines the amount of time required for gel
formation.
[0033] Time Required for Gel Formation
[0034] Embodiments of the gels disclosed herein may be prepared by
combining a gelling agent and a crosslinking agent in an aqueous
solution. In some embodiments, a gel may form immediately upon
mixing the gelling agent and the crosslinking agent. In other
embodiments, a gel may form within 1 minute of mixing; within 5
minutes of mixing in other embodiments; within 30 minutes of mixing
in other embodiments. In some embodiments, a gel may form within 1
hour of mixing; within 8 hours in other embodiments; within 16
hours in other embodiments; within 80 hours in other embodiments;
within 120 hours in yet other embodiments.
[0035] pH
[0036] In some embodiments, the gelling agent and the crosslinking
agent may be reacted in a medium having a pH greater than 4. In
other embodiments, the gelling agent and the crosslinking agent may
be reacted in a medium having a pH greater than 6; a pH greater
than 7 in other embodiments; a pH greater than 8 in other
embodiments; a pH greater than 9 in yet other embodiments.
[0037] Reagents which may be used to adjust the pH may include
alkali metal hydroxides, such as sodium hydroxide, potassium
hydroxide, calcium hydroxide, and rubidium hydroxide, lithium
hydroxides, benzyltrimethylammonium hydroxides, and the partially
neutralized salts of organic acids, such as tri-sodium
ethylenediaminetetraacetic acid. In some embodiments, the alkali
metal hydroxide, pH adjusting agent, or buffer, may act as a
catalyst, effecting or enhancing the crosslinking reaction between
the gelling agent and the crosslinking agent.
[0038] Water Concentration
[0039] In some embodiments, a solution of gelling agent(s) and
crosslinking agent(s) in water may initially have a varied
viscosity to obtain a desired degree of flow sufficient for
decreasing the flow of water through or increasing the load-bearing
capacity of a formation. The viscosity of the solution may be
varied by increasing or decreasing the amount of water relative to
the crosslinking and gelling agents, by employing viscosifying
agents, or by other techniques common in the art.
[0040] In some embodiments, the combined amount of gelling agents
and crosslinking agents may range from 0.5 to 100 weight percent,
based upon the total weight of water in the solution. In other
embodiments, the combined amount of gelling agents and crosslinking
agents may range from 5 to 100 weight percent, based upon the total
weight of water in the solution; from 20 to 70 weight percent in
other embodiments; from 25 to 65 weight percent in yet other
embodiments. As used herein, total weight of water is exclusive of
any additional water added with pH adjusting reagents.
[0041] The gelling agent and the crosslinking agent may react to
form gel beads. For example, in some embodiments, bead formation
may be effected by agitation of the solution. In other embodiments,
bead formation may be effected by forming an emulsion or suspension
of the reactants in water. In certain embodiments, an emulsion or
suspension may be formed using an organic solvent, emulsifying
agents, or combinations thereof.
[0042] Hardness
[0043] The reaction of the gelling agent and the crosslinking agent
may produce gels having a consistency ranging from a viscous sludge
to a hard gel. In some embodiments, the reaction of the gelling
agent and the crosslinking agent may result in a soft elastic gel.
In other embodiments, the reaction may result in a firm gel; in a
hard gel in yet other embodiments. The hardness of the gel is the
force necessary to break the gel structure, which may be quantified
by measuring the force required for a needle to penetrate the
crosslinked structure. Hardness is a measure of the ability of the
gel to resist to an established degree the penetration of a test
needle driven into the sample at a constant speed.
[0044] Hardness may be measured by using a Brookfield QTS-25
Texture Analysis Instrument. This instrument consists of a probe of
changeable design that is connected to a load cell. The probe may
be driven into a test sample at specific speeds or loads to measure
the following parameters or properties of a sample: springiness,
adhesiveness, curing, breaking strength, fracturability, peel
strength, hardness, cohesiveness, relaxation, recovery, tensile
strength burst point, and spreadability. The hardness may be
measured by driving a 2.5 mm diameter. cylindrical, flat faced
probe into the gel sample at a constant speed of 30 mm per minute.
When the probe is in contact with the gel, a force is applied to
the probe due to the resistance of the gel structure until it
fails, which is recorded via the load cell and computer software.
As the probe travels through the sample, the force on the probe and
the depth of penetration are measured. The force on the probe may
be recorded at various depths of penetration, such as 20, 25, and
30 mm, providing an indication of the gel's overall hardness. For
example, the initial peak force may be recorded at the point the
gel first fails, close to the contact point, followed by recording
highest and lowest values measured after this point where the probe
is travelling through the bulk of the gel.
[0045] In some embodiments, the resulting gel may have a hardness
value from 2 to 20000 gram-force. In other embodiments, the
resulting gel may be a soft elastic gel having a hardness value in
the range from 2 to 20 gram-force. In other embodiments, the
resulting gel may be a firm gel having a hardness value from 20 to
100 gram-force. In other embodiments, the resulting gel may range
from hard to tough, having a hardness value from 100 to 20000
gram-force; from 300 to 15000 gram-force in other embodiments; from
500 to 10000 gram-force in yet other embodiments; from 1000 to 6000
gram-force in yet other embodiments.
[0046] In other embodiments, the hardness of the gel may vary with
the depth of penetration. For example, the gel may have a hardness
of 300 gram-force or greater at a penetration depth of 20 mm in
some embodiments. In other embodiments, the gel may have a hardness
of 1000 gram-force or greater at a penetration depth of 20 mm;
3,000 gram-force or greater at a penetration depth of 20 mm in
other embodiments; and 5000 gram-force or greater at a penetration
depth of 25 mm in yet other embodiments.
[0047] With respect to the variables listed above (i.e.
temperature, time, etc.), those having ordinary skill in light of
the disclosure will appreciate that, by using the present
disclosure as a guide, properties may be tailored as desired.
[0048] Viscosity
[0049] The viscosity of the gel composition may be affected by the
concentrations of one or more of the gelling agent, viscosifier,
and solids present in the composition. As the concentrations of the
gelling agent, viscosifier, or solids increase, the viscosity of
the gel composition will increase. In some embodiments, the
concentration of the gelling agent may range from 8-25% by weight.
In other embodiments, the concentration of the gelling agent may
range from 10-20% by weight. In yet other embodiments, the
concentration of the gelling agent may range from 11-17%.
[0050] Viscosity may be measured by using a Brookfield DV-II+
Viscometer. One of skill in the art will appreciate that the
viscosity measurements will be dependent upon the temperature of
the gel composition, the type of spindle, and the number of
revolutions per minute. The viscosity ranges disclosed herein were
measured at 20.degree. C. using a Brookfield DV-II+ Viscometer with
a LV2 spindle. The viscosity may be measured by lowering the
viscometer into the center of the sample until the spindle is
immersed the middle of the immersion mark. Care should be taken not
to trap air under the spindle. The viscometer can be started after
adjusting the viscometer to the desired RPM. If more than one RPM
is to be used, the viscometer should be started at the lowest
desired RPM. This reduces the amount of shear introduced to the
sample, resulting in more accurate readings at lower RPM's.
[0051] In some embodiments, the mixing of the gelling agent and the
crosslinking agent may produce gel compositions having an initial
viscosity ranging from approximately 500 centipoise to 20,000
centipoise measured at 20.degree. C. using an LV2 spindle at low
rotational speeds (12 rpm or less). In other embodiments, the
mixing of the gelling agent and the crosslinking agent may produce
gel compositions having an initial viscosity ranging from
approximately 1000 centipoise to 5,000 centipoise measured at
20.degree. C. using an LV2 spindle at low rotational speeds (12 rpm
or less). As used herein, initial viscosity refers to the viscosity
of the composition prior to substantial reaction of the
crosslinking agent and gelling agent.
[0052] Applications
[0053] Some embodiments of the gels disclosed herein may be formed
in a one-solution single component system, where the crosslinking
agent(s) are premixed with a solution of the gelling agent
(material to be crosslinked) immediately prior to placement or
injection, thus maximizing the amount of time the composition
remains liquid before gel formation. The gel times may be adjusted
by changing the quantity of water in the solution. One of skill in
the art will appreciate that the gel times may also be adjusted by
other formulation variables such as pH. Other embodiments of the
gels disclosed herein may also be formed in a two-component system,
where one reagent, the crosslinking or gelling agent, may be placed
in the wellbore or the near-wellbore region where it may then be
contacted by the other reagent, either the crosslinking or gelling
agent as required.
[0054] Embodiments of the gels disclosed herein may be used in
applications including: as an additive in drilling muds; as an
additive for enhancing oil recovery (EOR); as one additive in loss
circulation material (LCM) pills; wellbore (WB) strengthening
treatments; soil stabilization; as a dust suppressant; as a water
retainer or a soil conditioner; as hydrotreating (HT) fluid loss
additives, and others.
[0055] Use in Drilling Muds
[0056] Drilling fluids or muds typically include a base fluid (for
example water, diesel or mineral oil, or a synthetic compound),
weighting agents (for example, barium sulfate or barite may be
used), bentonite clay, and various additives that serve specific
functions, such as polymers, corrosion inhibitors, emulsifiers, and
lubricants. Those having ordinary skill in the art will recognize
that a number of different muds exist, and limitations on the
present invention is not intended by reference to particular types.
During drilling, the mud is injected through the center of the
drill string to the drill bit and exits in the annulus between the
drill string and the wellbore, fulfilling, in this manner, the
cooling and lubrication of the bit, casing of the well, and
transporting the drill cuttings to the surface.
[0057] The gels disclosed herein may be used as an additive in
drilling mud. In some embodiments, the gels may form a filter cake
or one component of a filter cake that forms along the wellbore as
drilling progresses. The gels contained in the drilling fluid may
be deposited along the wellbore throughout the drilling process,
potentially strengthening the wellbore by stabilizing shale
formations and other sections encountered while drilling. Improved
wellbore stability may reduce the occurrence of stuck pipe, hole
collapse, hole enlargement, lost circulation, and may improve well
control.
[0058] Wellbore stability may also be enhanced by the injection of
a moderate viscosity mixture of a gelling agent and a crosslinking
agent into formations along the wellbore. The mixture may then
continue to react, strengthening the formation along the wellbore
upon gellation of the mixture.
[0059] In other embodiments, the gels disclosed herein may aid in
lifting solid debris from tubing walls and through the tubing
annulus. Hard gels circulating through the drill pipe during
drilling may scrape and clean the drill pipe, removing any pipe
scale, mud, clay, or other agglomerations that may have adhered to
the drill pipe or drill tubing. In this manner, the drill pipe may
be maintained free of obstructions that could otherwise hinder
removal of drilled solids from the drill pipe during drilling.
[0060] Enhanced Oil Recovery
[0061] Embodiments of the gels disclosed herein may be used to
enhance secondary oil recovery efforts. In secondary oil recovery,
it is common to use an injection well to inject a treatment fluid,
such as water or brine, downhole into an oil-producing formation to
force oil toward a production well. Thief zones and other permeable
strata may allow a high percentage of the injected fluid to pass
through only a small percentage of the volume of the reservoir, for
example, and may thus require an excessive amount of treatment
fluid to displace a high percentage of crude oil from a
reservoir.
[0062] To combat the thief zones or high permeability zones of a
formation, embodiments of the gels disclosed herein may be injected
into the formation, Gels injected into the formation may partially
or wholly restrict flow through the highly conductive zones. In
this manner, the gels may effectively reduce channeling routes
through the formation, forcing the treating fluid through less
porous zones, and potentially decreasing the quantity of treating
fluid required and increasing the oil recovery from the
reservoir.
[0063] In other embodiments, gels may also be formed in situ within
the formation to combat the thief zones. Gelling agents may be
injected into the formation, allowing the gelling agents to
penetrate further into the formation than if a gel was injected.
The crosslinking agents may then be injected, causing the
previously injected gelling agents to crosslink within the
formation. By forming the gels in situ in the formation, it may be
possible to avert channeling that may have otherwise occurred
further into the formation, such as where the treatment fluid
traverses back to the thief zone soon after bypassing the injected
gels as described above.
[0064] LCM Pills
[0065] As mentioned above, gels disclosed herein may be used as one
component in a drilling fluid. The gels may form part of a filter
cake, minimizing seepage of drilling fluids to underground
formations and lining the wellbore. As another example, embodiments
of the gels disclosed herein may be used as one component in loss
circulation material (LCM) pills that are used when excessive
seepage or circulation loss problems are encountered, requiring a
higher concentration of loss circulation additives. LCM pills are
used to prevent or decrease loss of drilling fluids to porous
underground formations encountered while drilling.
[0066] In some embodiments, the crosslinking agent and gelling
agent/material may be mixed prior to injection of the pill into the
drilled formation. The mixture may be injected while maintaining a
low viscosity, prior to gel formation, such that the gel may be
formed downhole. In other embodiments, the gelling material and
crosslinking agent may be injected into the formation in separate
shots, mixing and reacting to form a gel in situ (in the formation
following injection of the LCM pill shots). In this manner,
premature gel formation may be avoided.
[0067] For example, a first mixture containing a gelling agent may
be injected into the wellbore and into the lost circulation zone. A
second mixture containing a crosslinking agent and/or pH modifier
may be injected, causing the gelling agent to crosslink in situ to
the point that the gel expands in size. The expanded and hardened
gel may plug fissures and thief zones, closing off the lost
circulation zone.
[0068] Soil Stabilization
[0069] Gels described herein may be used as one component of a soil
stabilizer. For example, lignosulfonates may be used for
stabilizing road base courses and the like. Pulverized soil may be
mixed and worked with the stabilizing composition in a single or
multiple layer, compacting each layer as it is laid down. The
compaction may be by any suitable method such as rubber-tied
rollers or sheepsfoot rollers. The amount of stabilizing
composition used depends on the type of soil, moisture content and
other factors. The exact amount of stabilizing composition and the
amount of water dilution vary with soil type, moisture content and
other factors.
[0070] Dust Suppressant
[0071] Gels described herein may also be utilized for dust control,
dust suppression, dust palliative treatment, road stabilization and
many other dust binding applications. The lignin molecule functions
by adsorbing on the substrate and the binding effect results from
intermolecular forces between the lignin molecule and the
substrate. The lignin molecule is unique as it has several
different polar groups and aromatic systems. This increases the
affinity of the molecule which results in improved adhesion, and
makes it suitable for a wide range of substrates.
[0072] The binding property of lignin-based products may be
utilized in many types of dust control and dust prevention, such as
dust-suppression in roads, parking lots, racing tracks, quarries,
paddocks, and construction sites, dust-palliative or dust
prevention treatment of public and private roads, road and
soil-stabilization of secondary roads and areas, sand dune and
earth stabilization on areas to be kept free from dust and wind
erosion, and others.
[0073] For example, to prevent the loss of road surface fines and
prolong the useful driving life of unpaved roads, dust control
measures are usually employed before maintenance is required. The
primary dust suppressants in use are: water (fresh and sea),
chloride compounds, lignin derivatives, and resinous adhesives.
When used as dust suppressant, the lignin polymers act as glue
binding the soil particles together.
[0074] Gels disclosed herein may be used in other processes,
including the aforementioned applications such as water retainers,
soil conditioners, and hydrotreating (HT) fluid loss additives. It
is further contemplated that gels described herein may be useful in
other processes and applications known to those skilled in the
art.
EXAMPLES
Example 1
[0075] Samples 1-4 were prepared from a natural polyphenol powder
extract derived from quebracho (Colatan GTH, available from
Unitan). Samples 5 and 6 were prepared from a lignosulfonate
(Spersene CF, available from MI SWACO.phi.). These gelling agents
were crosslinked using either ethylene glycol diglycidyl ether
(EGDGE) (available from Sigma Aldrich) or a trifunctional aziridine
(trimethylolpropane tris(beta-ethyleniminopropionate) (TMPTEP),
available from BASF) as the crosslinking agent, as detailed in
Table 1. Comparative Samples 1 and 2 (CS1 and CS2) were prepared
from lignosulfonate and quebracho extract crosslinked with sodium
dichromate. The amount of natural polyphenol powder extract or
lignosulfonate given in Table 1 for each respective sample was
mixed with 10 mL water and the respective cross linking agent. The
pH of the mixture was adjusted to the desired level using sodium
hydroxide (available from Sigma Aldrich). The mixtures were then
placed in 25 mL screw top glass vials and aged under static
conditions at 70.degree. C. in a temperature controlled fan
assisted oven. The solution was observed during the aging process,
with the observations as noted in Table 1.
[0076] The strength and quality of the resulting gels were measured
following the aging process. Hardness is a measure of the ability
of the gel to resist to an established degree the penetration of a
test probe connected to a load cell driven at a constant speed into
the sample. Hardness was measured by driving a 2.5 mm diameter
needle probe into the gel sample at a speed of 30 mm per minute, as
described above with reference to the Brookfield Texture Analysis
QTS-25 Instrument. The probe was set at a standard start position
for the test above the sample in the glass vial. The test was
started and the probe was allowed to travel 40 mm, penetrating
nearly the full depth of the sample in the glass vial. The force on
the probe and the depth of penetration were recorded via computer
logging software. The results in Tables 1 and 2 present the
experimental results for the force on the probe that was recorded
at 20, 25, and 30 mm depths of penetration from the initial
starting position of the probe.
TABLE-US-00001 TABLE 1 Sample 1 2 3 4 5 6 CS1 CS2 Gelling Agent:
Quebracho extract (g) 3 3 5 5 -- -- 3 -- Lignosulphonate (g) -- --
-- -- 5 5 -- 3 Cross Linking Agent: EGDGE 0.5 1 0.5 1 1 -- -- --
TMPTEP -- -- -- -- -- 0.5 -- -- Sodium Dichromate -- -- -- -- -- --
0.5 0.5 pH (adjusted with caustic) 9.5 9.5 9.5 9.5 9.5 8.5
Observations at: 10 minutes Liquid Liquid Liquid Liquid Gel Paste
Liquid 30 minutes Thin Paste Liquid liquid 35 minutes Gel Liquid
Gel Liquid Gel Paste Liquid End of aging process Firm Hard Hard
Hard Soft Soft Crumbly Very gel Gel Gel Gel Elastic Elastic Paste
Weak Gel Gel Gel Aging Time (h) 16 80 80 80 80 80 16 16 Hardness
(gram-force) at depth of: 20 mm 42 324 1008 3374 9 5 20 1 25 mm 36
1022 1149 5000 11 3 19 2 30 mm 40 857 1265 Off-scale 14 3 18 2
[0077] Samples 1-4, each produced with quebracho extract, resulted
in a good gel or a hard gel after the aging process. Comparing
Sample 1 to Sample 2, a harder gel was formed when the amount of
crosslinking agent was doubled; a similar conclusion may be drawn
by comparing Sample 3 to Sample 4. Comparing Samples 1 to Sample 2,
and Sample 2 to Sample 4, increasing the amount of gelling agent
relative to the amount of water (constant at 10 mL), a harder gel
was formed by using less water relative to the gelling agent.
Additionally, Samples 1-6, gels produced from lignosulfonate and
quebracho extract, are comparable to or harder than gels produced
using a dichromate crosslinking agent.
[0078] Samples 7-9 were prepared from drilling starch. Sample 10
was prepared from a difunctional amine (JEFFAMINE.RTM. D230, a
polyoxyalkyleneamine available from Huntsman). These gelling agents
were crosslinked with EGDGE, aged, and analyzed in a manner similar
to that described above for Samples 1-6.
TABLE-US-00002 TABLE 2 Sample 7 8 9 10 Gelling Agent: Drilling
Starch 0.7 0.7 0.7 -- Jeffamine D230 -- -- -- 2.0 Cross Linking
Agent: EGDGE 1.0 1.0 1.0 3.0 pH 10.0 10.0 10.0 11 (Adjusted with
(Adjusted with (Adjusted with (Unadjusted) caustic) 0.5 g Trisodium
1.0 g Trisodium EDTA/Caustic) EDTA/Caustic) Observations at: 10
minutes Liquid Liquid Liquid Liquid 25 minutes Liquid -- -- Gel 1
hour 30 minutes Liquid Soft Gel Soft Gel Gel End of aging process
Liquid (pH 8.1) Soft Gel Soft Gel Firm Gel Aging Time (h) 20 20 20
16 Hardness (gram-force) at depth of: 20 mm -- 9 14 111 25 mm --
11.8 18 60 30 mm -- 48.2 18 72
[0079] Samples 7-10 demonstrate that pregelatinized starch, and di-
and tri-functional amine based materials may also be crosslinked
with EGDGE. Further, Samples 7-9 illustrate the use of an effective
pH buffer, as the sample without the trisodium EDTA buffer did not
gel.
Example 2
[0080] Table 3 details an aqueous gel formulated to illustrate the
effect of increasing the concentration of the gelling agent. These
samples were prepared from a lignosulfonate (Lignotech D1834)
gelling agents crosslinked using EGDGE, as detailed in Table 3. The
amount of lignosulfonate given in Table 3 for each respective
sample was mixed with 50 mL water and the EGDGE. The pH of the
mixture was adjusted to the desired level using sodium hydroxide.
The components, apart from the STARCARB, were mixed on a low shear
paddle mixer until homogeneous for approximately 15 to 30 minutes.
The viscosities were then measured on the viscometer after a period
of sixty seconds in order to make measurements more consistent by
giving the spindle time to release entrapped air bubbles that can
cause interference.
TABLE-US-00003 TABLE 3 6.2% w/w 11.7% w/w 16.6% % w/w Gelling Agent
Gelling Agent Gelling Agent Quantity Wt % Quantity Wt % Quantity Wt
% Product Function SG (mL) comp (mL) comp (mL) comp Water
Solvent/liquid 1 50.0 44.6% 50.0 42.0% 50.0 39.6% phase Degussa
Fumed silica 3 0.2 0.6% 0.2 0.6% 0.2 0.5% Aerosil 200 viscosifier,
suspending, and reinforcing agent Lignotech Lignosulphonate 1.15
6.1 6.2% 12.2 11.7% 18.3 16.6% D1834 gelling agent STARCARB Calcium
2.7 17.6 42.4% 17.6 39.9% 17.6 37.7% Carbonate bridging solids/
weighting agent CVC Crosslinking 1 3.7 3.3% 3.7 3.1% 3.7 2.9% EGDGE
Agent Huntsman Polyetheramine 1 3.2 2.9% 3.2 2.7% 3.2 2.5% XGJ502
co-gelling agent TOTALS 80.8 100% 86.9 100% 93.0 100% pH 11.6 11.4
11.3
[0081] The viscosity was measured using a Brookfield DV-II+
Viscometer using spindle LV2 at 60 rpm at 20.degree. C. Table 4
details the resulting viscosity for the 6.2, 11.7 and 16.6% w/w
gelling agent samples.
TABLE-US-00004 TABLE 4 Sample Viscosity (Cps) 6.2% w/w Gelling
Agent 8.5 11.7% w/w Gelling Agent 32.0 16.6% w/w Gelling Agent
166.0
[0082] The results in Table 4 illustrate that the viscosity of the
aqueous gel increases as more gelling agent is added to the
mixture.
[0083] Table 5 details the viscosity results when STARCARB is added
to the formulations of Table 3.
TABLE-US-00005 TABLE 5 Viscosity (Cps) Hardness (g) 0.6 0.3 Initial
Bulk Sample 12 RPM 6 RPM RPM RPM Hardness Range 6.2% w/w 80 90 NR*
NR* 4 Gelling Agent 11.7% w/w 665 1090 5800 11800 364 355-571
Gelling Agent 16.6% w/w 1400 1700 5000 7400 869 819-1531 Gelling
Agent *The viscosities were too low to accurately measure at low
speeds, a consequence of the low viscosity was the bridging solids
settling out of the mixture
[0084] The results in Table 5 illustrate the importance of having
sufficient viscosity to suspend any solids present in the
composition. At viscosities lower than approximately 500 centipoise
measured at 20.degree. C. at low rotational speeds, the solids
settle out of the composition. Further, increasing the amount of
gelling agent, which increases the viscosity of the composition,
contributes to strong gels. Thus, it is desirable to add sufficient
gelling agents to produce a gel composition with an initial
viscosity of at least 500 centipoise measured at 20.degree. C.
using an LV2 spindle at low rotational speeds (12 rpm or less).
[0085] Advantageously, embodiments disclosed herein provide for the
formation of a lignin, lignosulfonate, tannin, or tannic acid based
gel formed using low or non-toxic crosslinking agents. These gels
have the benefit of being formed from materials that provide a
better health, safety, and environmental profile as compared
dichromates, aldehydes, and epichlorohydrins. The crosslinking
agents disclosed herein may also provide a low-cost alternative for
the formation of desired gels.
[0086] Embodiments of the gels disclosed herein may form a soft
elastic gel. Other embodiments of the gels disclosed herein may
form a hard gel. In particular embodiments, the gels disclosed
herein may be of equivalent or greater hardness than lignin or
lignosulfonate gels formed from dichromates.
[0087] While the invention has been described with respect to a
limited number of embodiments, those skilled in the art, having
benefit of this disclosure, will appreciate that other embodiments
can be devised which do not depart from the scope of the invention
as disclosed herein. Accordingly, the scope of the invention should
be limited only by the attached claims.
[0088] All priority documents are herein fully incorporated by
reference for all jurisdictions in which such incorporation is
permitted. Further, all documents cited herein, including testing
procedures, are herein fully incorporated by reference for all
jurisdictions in which such incorporation is permitted to the
extent such disclosure is consistent with the description of the
present invention.
* * * * *