US007727937B2

(12) United States Patent (10) Patent No.: US 7,727,937 B2

Pauls et al. (45) Date of Patent: *Jun. 1, 2010
(54) ACDIC TREATMENT FLUIDS COMPRISING 6,525,011 B2 2/2003 Brezinski .................... 510,253
XANTHAN AND ASSOCATED METHODS 6,527,051 B1 3/2003 Reddy et al. ................ 166,300
6,534,448 B1 3/2003 Brezinski ..................... 507/90
(75) Inventors: Richard W. Pauls, Duncan, OK (US); 6,547,871 B2 4/2003 Chatterji et al. ............. 106,672
Thomas D. Welton, Duncan, OK (US) 6,554,071 B1 4/2003 Reddy et al. ................ 166,293
(73) Assignee: Halliburton Energy Services, Inc., 6,566,310 B2 5/2003 Chan .......................... 507,211
Duncan, OK (US) 6,640,898 B2 1 1/2003 Lord et al. .................. 166,300
6,706,668 B2 3/2004 Brezinski .................... 507/269
(*) Notice: Subject to any disclaimer, the term of this 6,767,869 B2 7/2004 DiLullo et al.
patent is extended or adjusted under 35 6,806,235 B1 10/2004 Mueller et al. .............. 507 138
U.S.C. 154(b) by 279 days. B2 4/2005 Todd et al. .................. 166/312
6,877,563
This patent is Subject to a terminal dis 6,987,083 B2 1/2006 Phillippi et al. ............. 507,213
claimer. 7,021,383 B2 4/2006 Todd et al. .................. 166/307
7,159,659 B2 1/2007 Welton et al. ............... 166/307
(21) Appl. No.: 11/891,542 7, 195,068 B2 3, 2007 Todd
7,299,876 B2 11/2007 Lord et al.
(22) Filed: Aug. 10, 2007
B2 3/2008 Fraser
7,345,013
(65) Prior Publication Data 7,353,876 B2 4/2008 Savery et al.
7,353,879 B2 4/2008 Todd et al.
US 2007/028.1868 A1 Dec. 6, 2007
7,413,017 B2 8/2008 Nguyen et al.
Related U.S. Application Data 7,448450 B2 11/2008 Luke et al.
7,455, 112 B2 11/2008 Moorehead et al.
(63) Continuation-in-part of application No. 10/889,860, 7.461,697 B2 12/2008 Todd et al.
filed on Jul. 13, 2004, now abandoned, and a continu B2 1/2009 Pauls et al.
ation-in-part of application No. 1 1/118,028, filed on 7,475,728
7,484,564 B2 2/2009 Welton et al.
Apr. 29, 2005, now Pat. No. 7,621,334, and a continu
ation-in-part of application No. 1 1/117,959, filed on 7,497,258 B2 3/2009 Savery et al.
Apr. 29, 2005, now Pat. No. 7,547,665. 7,497,278 B2 3/2009 Schriener et al.

(51) Int. C.
C09K 8/60 (2006.01)
E2IB 43/16 (2006.01) (Continued)
(52) U.S. Cl. ................. 507/213; 166/305.1: 166/308.2: FOREIGN PATENT DOCUMENTS
507/209; 507/211
(58) Field of Classification Search ................. 507/213, EP 1617 O39 A1 1, 2006
507/211, 209; 166/305.1, 308.1, 308.2
See application file for complete search history.
(56) References Cited
(Continued)
U.S. PATENT DOCUMENTS
OTHER PUBLICATIONS
4,010,071 A 3/1977 Colegrove ... ... 435/72
4,265,673 A 5, 1981 Pace et al. ... 106.175.1 Biopolymers in Salt Solutions Technical Bulletin, Kelco Oil Filed
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5,916,849 A 6/1999 House ........................ 507/110
5,977,030 A 1 1/1999 House ........................ 507/110
5.996,694 A 12/1999 Dewprashadet al. ....... 166/294 Acidic treatment fluids used in industrial and/or subterranean
6,100,222 A 8/2000 Vollmer et al. .............. 507 113 operations, and more particularly, acidic treatment fluids
6,110,875 A 8/2000 Ton-Joe-Pin et al. ....... 507/2O1 comprising clarified Xanthan gelling agents, and methods of
6,123,159 A 9/2000 Brookey et al. ............... 175/72 use in industrial and/or Subterranean operations, are pro
6,148,917 A 1 1/2000 Brookey et al. . ... 166/301 vided. In one embodiment, the acidic treatment fluids com
6,302,209 B1 10/2001 Thompson etal 166,305.1 prise an aqueous base fluid, an acid, and a gelling agent
6,315,045 B1 11/2001 Brezinski ....... ... 166,300
6.422,326 B1 7/2002 Brookey et al. ............... 175/72 comprising clarified Xanthan.
6,444,316 Bl 9/2002 Reddy et al. ... ... 428,407
6,488,091 B1 12/2002 Weaver et al. ............... 166,300 20 Claims, 2 Drawing Sheets
 US 7,727,937 B2
Page 2

U.S. PATENT DOCUMENTS 2007/0078064 A1 4/2007 Munoz et al.

2007/0238623 A1 10, 2007 Saini et al.
7,506,689 B2 3/2009 Surjaatmadja et al. 2008, 0026955 A1 1/2008 Munoz et al.
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2007/0078063 A1 4/2007 Munoz, Jr. * cited by examiner
U.S. Patent Jun. 1, 2010 Sheet 1 of 2 US 7.727,937 B2

(o) Asoo’s Auereddv

U.S. Patent Jun. 1, 2010 Sheet 2 of 2 US 7.727,937 B2

(3) Asoos.A
 US 7,727,937 B2
1. 2
ACDIC TREATMENT FLUIDS COMPRISING treatment fluid may enable the development of wider frac
XANTHAN AND ASSOCATED METHODS tures so that the gelled acidic treatment fluid may delay the
interaction of the acid with an acid soluble component in the
CROSS-REFERENCE TO RELATED well bore or the formation. Moreover, gelling an aqueous
APPLICATIONS acidic treatment fluid may permit better fluid loss control.
Acidic treatment fluids used in Subterranean operations are
The present application is related to co-pending U.S. appli predominantly water-based fluids that comprise gelling
cation Ser. No. 1 1/891,538 entitled “Acidic Treatment Fluids agents that may increase their viscosities. These gelling
Comprising Xanthan and Associated Methods.” filed concur agents are usually biopolymers or synthetic polymers that,
rently herewith, and is a continuation-in-part of U.S. applica 10 when hydrated and at a Sufficient concentration, are capable
tion Ser. No. 10/889,860 filed on Jul. 13, 2004, now aban of forming a more viscous fluid. Common gelling agents
doned, and of U.S. application Ser. No. 1 1/118,028 filed on include polysaccharides (such as Xanthan), synthetic poly
Apr. 29, 2005, now U.S. Pat. No. 7,621,334, and of U.S. mers (such as polyacrylamide), and Surfactant gel systems.
application Ser. No. 11/117,959 filed on Apr. 29, 2005, now Acidic treatment fluids comprising Xanthan generally have
U.S. Pat. No. 7,547,665, the entire disclosures of which are 15 sufficient viscosity for lower temperature operations. At
incorporated herein by reference elevated temperatures (e.g., those above about 120° F. to
about 150°F), however, the viscosity of such xanthan treat
BACKGROUND ment fluids sometimes is diminished. Consequently, Xanthan
may not be a suitable gelling agent for acidic treatment fluids
The present invention relates to acidic treatment fluids used when those fluids are used in subterranean formations that
in industrial and/or Subterranean operations, and more par comprise elevated temperatures. Other gelling agents such as
ticularly, to acidic treatment fluids comprising clarified Xan synthetic gelling agents (e.g., polyacrylamides) have been
than gelling agents, and methods of use in industrial and/or used in Subterranean formations at these elevated tempera
Subterranean operations. tures, but often they are difficult to disperse and usually
Acidizing and fracturing procedures using acidic treatment 25 require considerable mixing or agitation to develop full vis
fluids are commonly carried out in Subterranean well forma cosity. Additionally, most conventional gelling agents,
tions to accomplish a number of purposes including, but not including guarand some synthetic polymers, may form acid
limited to, to facilitate the recovery of desirable hydrocarbons insoluble residues. Surfactant gel systems also have been
from the formation. As used herein, the term “treatment fluid used in Subterranean formations at these temperatures, but
refers to any fluid that may be used in a Subterranean appli 30 Such systems can be expensive, can be sensitive to impurities,
cation in conjunction with a desired function and/or for a and may require hydrocarbon breakers.
desired purpose. The term “treatment fluid does not imply
any particular action by the fluid or any component thereof. SUMMARY OF THE INVENTION
One commonly used aqueous acidic treatment fluid com
prises hydrochloric acid. Other commonly used acids for 35 The present invention relates to acidic treatment fluids used
acidic treatment fluids include hydrofluoric acid, acetic acid, in industrial and/or Subterranean operations, and more par
formic acid, citric acid, ethylene diamine tetra acetic acid ticularly, to acidic treatment fluids comprising clarified Xan
(“EDTA), glycolic acid, sulfamic acid, and derivatives or than gelling agents, and methods of use in industrial and/or
combinations thereof. Subterranean operations.
Acidic treatment fluids are used in various Subterranean 40 In one embodiment, the present invention provides meth
operations. For example, formation acidizing or “acidizing ods comprising: providing an acidic treatment fluid that com
is a method for, among other purposes, increasing the flow of prises an aqueous base fluid, an acid, and a gelling agent that
desirable hydrocarbons from a subterranean formation. In a comprises clarified Xanthan; and introducing the acidic treat
matrix acidizing procedure, an aqueous acidic treatment fluid ment fluid into a portion of a Subterranean formation.
is introduced into a subterranean formation via a well bore 45 In another embodiment, the present invention provides
therein under pressure so that the acidic treatment fluid flows methods of acidizing a portion of a subterranean formation
into the pore spaces of the formation and reacts with (e.g., comprising: providing an acidic treatment fluid that com
dissolves) the acid-soluble materials therein. As a result, the prises an aqueous base fluid, an acid, and a gelling agent that
pore spaces of that portion of the formation are enlarged, and comprises clarified Xanthan; contacting a portion of the Sub
the permeability of the formation may increase. The flow of 50 terranean formation with the acidic treatment fluid; and
hydrocarbons from the formation therefore may be increased allowing the acidic treatment fluid to interact with a compo
because of the increase in formation conductivity caused, nent of the Subterranean formation so that at least a portion of
interalia, by dissolution of the formation material. Infracture the component is dissolved.
acidizing procedures, one or more fractures are produced in In another embodiment, the present invention provides
the formation(s) and an acidic treatment fluid is introduced 55 methods of diverting fluids in a subterranean formation com
into the fracture(s) to etch flow channels therein. Acidic treat prising: providing an acidic treatment fluid comprising an
ment fluids also may be used to clean out well bores to aqueous base fluid, an acid, and agelling agent that comprises
facilitate the flow of desirable hydrocarbons. Other acidic clarified Xanthan; introducing the acidic treatment fluid into a
treatment fluids may be used in diversion processes and well well bore that penetrates the subterranean formation; and
bore clean-out processes. A specific example is filter cake 60 allowing at least a first portion of the acidic treatment fluid to
removal. penetrate into a portion of the Subterranean formation so as to
To increase the viscosity of an aqueous acidic treatment substantially divert a second portion of the acidic treatment
fluid, a suitable gelling agent may be included in the treatment fluid or another treatment fluid to another portion of the
fluid (often referred to as "gelling the fluid). Gelling an Subterranean formation.
aqueous acidic treatment fluid may be useful, among other 65 The features and advantages of the present invention will
purposes, to prevent the acid from becoming prematurely be readily apparent to those skilled in the art upon a reading of
spent and inactive. Additionally, gelling an aqueous acidic the description of the preferred embodiments that follows.
 US 7,727,937 B2
3 4
BRIEF DESCRIPTION OF THE DRAWINGS will only partially hydrate or will not hydrate at ambient
temperature. This form of clarified xanthan may be chemi
These drawings illustrate certain aspects of Some of the cally modified, chemically coated, genetically modified, or
embodiments of the present invention, and should not be used produced from a new strain of bacteria.
to limit or define the invention. In some embodiments, the present invention provides com
FIG. 1 illustrates viscosity data from an experiment involv positions and methods that may be especially suitable for use
ing an embodiment of the present invention. in well bores comprising a borehole temperature (“BHT”) of
FIG. 2 also illustrates viscosity data from an experiment up to about 300° F. In certain embodiments, the treating
involving an embodiment of the present invention. temperature may be below about 180° F. Typical Xanthans
10 show thermal degradation based on rheological measure
DESCRIPTION OF PREFERRED ments at about 140° F., and certain embodiments of the
EMBODIMENTS present invention show thermal degradation based on rheo
logical measurements at about 170° F. One skilled in the art
The present invention relates to acidic treatment fluids used will recognize that there are a number of instances where fluid
in industrial and/or Subterranean operations, and more par 15 may be used successfully at temperatures above the BHT
ticularly, to acidic treatment fluids comprising clarified Xan when cool-down is taken into account. The ability of the
than gelling agents, and methods of use in industrial and/or acidic treatment fluids of the present invention to maintain a
Subterranean operations. degree of Viscosity at Such elevated temperatures may be
In certain embodiments, the acidic treatment fluids of the affected by the time a particular fluid is exposed to such
present invention generally comprise an aqueous base fluid, temperatures. For example, in Some fracture acidizing appli
an acid, and a gelling agent of the present invention that cations, there may be a considerable fracture cool-down,
comprises clarified Xanthan. In certain embodiments, the which may enable utilization of an acidic treatment fluid of
term “clarified Xanthan refers to a Xanthan that has not been the present invention at BHT above the temperature limit at
treated, either chemically or otherwise, to affect its ability to which the fluid exhibits significant viscosity.
disperse and hydrate in fresh water or salt solutions, or 25 Although some potential advantages of the present inven
hydrate at a specific pH range. This definition controls the tion are discussed herein, this is in no way an exhaustive list
meaning of the term “clarified xanthan in the claims of this of potential advantages and does not comprise the universe of
application, particularly over any other definition found in objectives of the invention. One potential advantage of the
any reference, patent, or patent application, whether or not it many advantages of the fluids of the present invention is that
is referenced or incorporated by reference herein. In some 30 they may be shear thinning fluids (e.g., the Viscosity of the
embodiments, Suitable clarified Xanthans may have been fluid decreases with rate of shear). Another potential advan
treated with methods involving enzymes or any other suitable tage is that the gelling agents of the present invention com
method, inter alia, to remove any debris from the Xanthan prising clarified Xanthan may impart a higher regain of per
polymer. meability to a fluid than conventional gelling agents. Another
In some embodiments, the term “clarified Xanthan refers 35 potential advantage is that the gelling agents of the present
to a Xanthan that has a flow rate of at least about 200 ml in 2 invention comprising clarified Xanthan may result in fluids
minutes at ambient temperature in a filtering laboratory test having a higher viscosity than conventional gelling agents at
on a Baroid Filter Press using 40 psi of differential pressure the same concentration. Another potential advantage is that
and a 9 cm Whatman filter paper having a 2.7L pore size. In the fluids may not leave undesirable residues in the formation
Some embodiments, Suitable clarified Xanthans are capable of 40 once the fluid has been broken. Additionally, the gelling
hydrating in a brine to produce an increase in viscosity. agents comprising clarified Xanthan may present a cost sav
In some embodiments, Suitable clarified Xanthans may ings over some conventional gelling agents (e.g., Surfactant
have been treated with enzymes or other suitable methods to based gelling agents) for acidic treatment fluid applications.
remove residual cellular structures, such as cell walls, from a Other potential advantages may include ease of mixing over
standard Xanthan. In some embodiments, suitable clarified 45 other gelling agents (should not lump and therefore may not
Xanthans may be produced from genetically modified or require adjusting the pH for polymer dispersion), potential
bioengineered strains of bacteria or other strains of bacteria capability of gelling any brine at a wider range of pH levels,
that allow the clarified xanthan to have improved functional potential relative ease of polymer hydration in the presence of
properties such as filterability, turbidity, etc. In one embodi certain common contaminants, potential capability of gelling
ment, Suitable clarified Xanthans may be modified by genetic 50 formation brine (potentially saving time and cost), and poten
engineering or bacteria selection or the result of chemical tial ability to be directly added to an acid for gelation. Other
treatment or derivatization of a Xanthan. An example of Such potential advantages may be evident to one of ordinary skill in
a modification would be where a portion of the xanthan is the art with the benefit of this disclosure.
oxidized or hydrolyzed. In one embodiment, the clarified The acidic treatment fluids of the present invention may be
Xanthan may be modified. Such as nonacetylated and/or non 55 useful in a wide variety of subterranean treatment operations
pyruvylated Xanthan. As used herein, “nonacetylated” means in which acidic treatment fluids may be suitable. For example,
having fewer acetyl groups than typical Xanthan, whether the an acidic treatment fluid of the present invention having a
difference is the result of genetic engineering or bacteria sufficient viscosity may be used to divert the flow of fluids
selection or the result of chemical treatment of a typical present within a Subterranean formation (e.g., formation flu
Xanthan. As used herein, "nonpyruvylated” means having 60 ids, other treatment fluids) to other portions of the formation,
fewer pyruvyl groups, whether the difference is the result of for example, by invading the higher permeability portions of
genetic engineering or bacteria selection or the result of the formation with a fluid that has high viscosity at low shear
chemical treatment of a Xanthan. Furthermore, as used herein, rates. The methods and acidic treatment fluids of the present
nonpruVylated and nonacetylated are intended to encompass invention may be used during or in preparation for any Sub
depruVylated and deacetylated, respectively. Another 65 terranean operation wherein a fluid may be used. Suitable
example of modified Xanthan is partially oxidized Xanthan. Subterranean operations may include, but are not limited to,
Suitable clarified xanthan may also be present in a form that acidizing treatments (e.g., matrix acidizing or fracture acidiz
 US 7,727,937 B2
5 6
ing), well bore clean-out treatments, and other Suitable opera tion Publication No. 2006/0014648 by Milson et al., the rel
tions where a treatment fluid of the present invention may be evant disclosure of which is herein incorporated by reference.
useful. Optionally, the gelling agents of the present invention may
In certain embodiments, the treatment fluids of the present comprise an additional biopolymer if the use of the clarified
invention may have a pH of about 4 or less. In certain embodi Xanthan and the biopolymer produces a desirable result, e.g.,
ments (e.g., where the acid comprises hydrochloric acid), the a synergistic effect. Suitable biopolymers may include
polysaccharides and galactomannan gums. Depending on the
treatment fluids may have a pH of about 1 or less. In certain application, one biopolymer may be more Suitable than
embodiments (e.g., where the acid comprises an organic another. One of ordinary skill in the art with the benefit of this
acid), the treatment fluids may have a pH of about 1 to about 10 disclosure will be able to determine ifa biopolymer should be
4.
included for a particular application based on, for example,
The acidic treatment fluids of the present invention may the desired viscosity of the viscosified treatment fluid and the
vary widely in density, depending on the chosen application. bottom hole temperature (“BHT”) of the well bore.
One of ordinary skill in the art with the benefit of this disclo The aqueous base fluids of the acidic treatment fluids of the
Sure will recognize the particular density that is most appro 15 present invention generally comprise fresh water, salt water,
priate for a particular application. In certain embodiments, sea water, a brine (e.g., a Saturated salt water or formation
the acidic treatment fluids of the present invention will have a brine), or a combination thereof. Other water sources may be
density of about 8.3 pounds per gallon (ppg) to about 19.2 used, including those comprising monovalent, divalent, or
ppg. The desired density for a particular acidic treatment fluid trivalent cations (e.g., magnesium, calcium, Zinc, or iron) and,
may depend on characteristics of the Subterranean formation where used, may be of any weight. If a water source is used
and/or fluids in the well bore. The density of a treatment fluid that contains such divalent or trivalent cations in concentra
of the present invention may be adjusted, among other ways, tions sufficiently high to be problematic, then such divalent or
by adding salts and/or brines. The types of salts or brines used trivalent salts may be removed, either by a process Such as
to achieve the desired density of the acidic treatment fluid can reverse osmosis, or by raising the pH of the water in order to
be chosen based on factors such as compatibility with the 25 precipitate out Such divalent salts to lower the concentration
formation, crystallization temperature, and compatibility of such salts in the water before the water is used. Another
with other treatment and/or formation fluids. Availability and method would be to include a chelating agent to chemically
environmental impact also may affect this choice. bind the problematic ions to prevent their undesirable inter
The gelling agents used in the acidic treatment fluids of the actions with the clarified Xanthan. Suitable chelants include,
present invention comprise a clarified Xanthan. Suitable clari 30 but are not limited to, citric acid or sodium citrate, ethylene
fied Xanthans should impart some degree of pseudoplastic diamine tetra acetic acid ("EDTA'), hydroxyethyl ethylene
rheology or shearthinning behavior to a fluid. Suitable clari diamine triacetic acid (“HEDTA'), dicarboxymethyl
fied xanthans also may be soluble in hot or cold water, and glutamic acid tetrasodium salt (“GLDA), diethylenetri
may be stable over a range of pH levels and temperatures. aminepentaacetic acid (“DTPA), propylenediaminetet
Additionally, they may be compatible with and stable in sys 35 raacetic acid (“PDTA), ethylenediaminedi(o-hydroxyphe
tems containing salts, e.g., they may fully hydrate in Systems nylacetic) acid (“EDDHA), glucoheptonic acid, gluconic
comprising salts. Moreover, Suitable clarified Xanthans may acid, and the like, and nitrilotriacetic acid (“NTA'). Other
provide good Suspension for particulates often used in Sub chelating agents also may be suitable. One skilled in the art
terranean applications, such as proppant or gravel, and may will readily recognize that an aqueous base fluid containing a
have good filterability. An example of a suitable clarified 40 high level of multi-valent ions should be tested for compat
Xanthan for use in conjunction with the compositions and ibility prior to use.
methods of the present invention is commercially available In some embodiments, the base fluids suitable for use in the
under the tradename “KELTROLR BT from CP Kelco, in acidic treatment fluids of the present invention may be a
various locations including Chicago, Ill. “FLOCON4800TM' foamed fluid (e.g., a liquid that comprises a gas such as
and “FLOCON 4800CTM are two other Xanthans commer 45 nitrogen, carbon dioxide, air or methane). As used herein, the
cially available from SNF Floerger, Andrézieux France, term “foamed also refers to fluids such as co-mingled fluids.
that may be suitable for use in conjunction with the present In certain embodiments, it may desirable that the base fluid is
invention. The xanthan taught by Pace in U.S. Pat. No. 4,265, foamed to, interalia, reduce the amount of base fluid that is
673 (the relevant disclosure of which is herein incorporated required, e.g. in water sensitive Subterranean formations, to
by reference) also may be suitable for use in conjunction with 50 reduce fluid loss to the subterranean formation, and/or to
the present invention. The amount of gelling agent compris provide enhanced proppant Suspension. In addition, in certain
ing clarified xanthan used in the acidic treatment fluids of the embodiments where the acidic treatment fluids of the present
present invention may vary from about 1 lb/Mgal to about 200 invention are used for fluid diversion, it may be desirable that
1b/Mgal. In some embodiments, the amount of gelling agent the acidic treatment fluid be foamed. While various gases can
comprising clarified Xanthan included in the treatment fluids 55 be utilized for foaming the acidic treatment fluids of this
of the present invention may vary from about 20 lb/Mgal to invention, nitrogen, carbon dioxide, and mixtures thereofare
about 100 lb/Mgal. In other embodiments, the amount of preferred. In examples of Such embodiments, the gas may be
gelling agent comprising clarified Xanthan included in the present in a acidic treatment fluid of the present invention in
treatment fluids of the present invention may vary from about an amount in the range of from about 5% to about 98% by
30 lb/Mgal to about 80 lb/Mgal. In certain embodiments, 60 volume of the treatment fluid, and more preferably in the
about 60 lb/Mgal of a gelling agent comprising clarified Xan range of from about 20% to about 80%. The amount of gas to
than is included in the treatment fluids of the present inven incorporate into the fluid may be affected by factors including
tion. In well bores comprising BHTs of 200°F. or more, 70 the viscosity of the fluid and wellhead pressures involved in a
lbs/Mgal or more of the gelling agent comprising clarified particular application. One example of a foamed fluid suitable
Xanthan may be used in a treatment fluid of the present inven 65 for use with the present invention are those disclosed in U.S.
tion. Clarified Xanthans that may be suitable for use in the patent application Ser. No. 1 1/506.703, the relevant disclo
present invention also are disclosed in U.S. Patent Applica sure of which is herein incorporated by reference.
 US 7,727,937 B2
7 8
If desired, the acidic treatment fluids of the present inven chosen should be compatible with the formation and should
tion may also be used in the form of an emulsion. An example have a sufficient density to provide the appropriate degree of
of a Suitable emulsion may comprise an aqueous base fluid well control. Additional salts may be added to a water source,
comprising a clarified Xanthan gelling agent and a suitable e.g., to provide a brine, and a resulting acidic treatment fluid,
hydrocarbon. In some embodiments, the emulsion may com having a desired density. The amount of salt that should be
prise approximately 30% of an aqueous base fluid and 70% of added should be the amount necessary for formation compat
a suitable hydrocarbon. In some embodiments, the external ibility, such as the amount necessary for the stability of clay
phase of the emulsion may be aqueous. In certain embodi minerals, taking into consideration the crystallization tem
ments, it may be desirable to use an emulsion to, inter alia, perature of the brine, e.g., the temperature at which the salt
reduce fluid loss to the subterranean formation, and/or to 10 precipitates from the brine as the temperature drops. Pre
provide enhanced proppant Suspension. Other benefits and ferred suitable brines may include seawater and/or formation
advantages to using emulsions in the methods of the present brines.
invention will be evident to one of ordinary skill in the art. Suitable acids for inclusion in the acidic treatment fluids of
The acidic treatment fluids of the present invention may the present invention include any acid suitable for use in a
vary widely in density. One of ordinary skill in the art with the 15 Subterranean application. Examples include hydrochloric
benefit of this disclosure will recognize the particular density acid, hydrofluoric acid, acetic acid, formic acid, citric acid,
that is most appropriate for a particular application. In some lactic acid, glycolic acid, Sulfamic acid, and derivatives and
embodiments, the density of the non-foamed acidic treatment combinations thereof. The term "derivative' is defined herein
fluids of the present invention generally may approximate the to include any compound that is made from one of the listed
density of water. In other embodiments, the density of the compounds, for example, by replacing one atom in the listed
non-foamed acidic treatment fluids of the present invention compound with another atom or group of atoms, rearranging
generally may range from about 8.3 pounds per gallon two or more atoms in the listed compound, ionizing one of the
(ppg) to about 30 ppg. One of ordinary skill in the art with listed compounds, or creating a salt of one of the listed com
the benefit of this disclosure will recognize that the density of pounds. The choice of aqueous base fluid and acid may be
any particular acidic treatment fluid of the present invention 25 chosen vis-a-vis the other, among other reasons, so that the
may also vary depending on the addition of certain additives, proper synergistic effect is achieved. The concentration and
including, but not limited to, inorganic salts, proppant, gas, type of acid selected may be based upon the function of the
fluid loss control additives, alcohols, glycols, and/or hydro acid (e.g., Scale removal, fracture acidizing, matrix acidizing,
carbons. Furthermore, the desired density for a particular removal of fluid loss filter cakes and pills, and the like),
acidic treatment fluid may depend on characteristics of the 30 compatibility with crude oil, and the mineralogy and tem
Subterranean formation, including, interalia, the hydrostatic perature of the formation. One should be mindful that certain
pressure required to control the fluids of the subterranean concentrations of acids may have a tendency to form precipi
formation during placement of the acidic treatment fluids, and tates upon spending, Such as formic acid.
the hydrostatic pressure which may damage the Subterranean Optionally, the gelling agents comprising clarified Xanthan
formation. For example, if the acidic treatment fluid remains 35 and acidic treatment fluids of the present invention may com
in the well bore, the density of the acidic treatment fluid may prise an additional biopolymer. In certain embodiments, the
be adjusted to, interalia, prevent the changing of position of use of the clarified Xanthan and the biopolymer may produce
a fluid relative to another fluid with a different density, a synergistic effect. Suitable biopolymers may include, but
thereby leaving the acidic treatment fluid at the correct place are not limited to, polysaccharides, galactomannan gums,
ment within the well bore. 40 Scleroglucan, diutan, clarified versions thereof, combinations
In some embodiments, the acidic treatment fluid may com thereof, and derivatives thereof. Derivatization of these
prise a brine. Brines suitable for use in some embodiments of biopolymers may involve, among other things, chemical
the present invention may include those that comprise treatment/modification, differences resulting from the result
monovalent, divalent, or trivalent cations. Some divalent or of genetic engineering, from the result of strain selection, and
trivalent cations, such as magnesium, calcium, iron, and Zinc, 45 the like. Moreover, “clarified versions of these biopolymers
may, in some concentrations and at Some pH levels, cause refers to a biopolymer that has not been treated, either chemi
undesirable crosslinking of a Xanthan polymer. If a water cally or otherwise, to affect its ability to disperse and hydrate
Source is used which contains such divalent or trivalent cat in fresh water or salt solutions, or hydrate at a specific pH
ions in concentrations Sufficiently high to be problematic, range. In some embodiments, Suitable clarified biopolymers
then such divalent or trivalent salts may be removed, either by 50 may have been treated with methods involving enzymes or
a process Such as reverse osmosis, or by raising the pH of the any other suitable method, inter alia, to remove any debris
water in order to precipitate out Such salts to lower the con from the biopolymer. A suitable source of diutan is “GEO
centration of such salts in the water before the water is used. VIS(R) XT,” which is commercially available from Kelco Oil
Another method would be to include a chelating agent to Field Group, Houston, Tex. Other suitable sources of diutan
chemically bind the problematic ions to prevent their unde 55 are “FDP-S848-07 and “FDP-S849-07 which are commer
sirable interactions with the Xanthan. As used herein, the term cially available from Halliburton Energy Services, Duncan,
“chelating agent' or “chelant' also refers to sequestering Okla. Depending on the application, one biopolymer may be
agents and the like. Suitable chelants include, but are not more Suitable than another. For example, an acidic treatment
limited to, citric acidorsodium citrate. Other chelating agents fluid containing an organic acid may require less of an addi
also are suitable. Brines, where used, may be of any weight. 60 tional biopolymer comprising Scleroglucan and/or diutan
Examples of suitable brines include calcium bromide brines, than an acidic treatment fluid containing hydrochloric acid.
Zinc bromide brines, calcium chloride brines, sodium chlo One of ordinary skill in the art with the benefit of this disclo
ride brines, sodium bromide brines, potassium bromide sure will be able to determine if a biopolymer should be
brines, potassium chloride brines, sodium nitrate brines, included for a particular application based on, for example,
Sodium formate brines, potassium formate brines, cesium 65 the desired viscosity of the acidic treatment fluid and the
formate brines, magnesium chloride brines, sodium Sulfate, bottom hole static temperature of the formation where the
potassium nitrate, mixtures thereof, and the like. The brine fluid is to be used. Another reason for using a mixture of
 US 7,727,937 B2
10
clarified Xanthan with Scleroglucan is that, under Some con nitrilopropionamide, commercially available under the trade
ditions, Scleroglucan may exhibit reduced regain permeabil name BE-3STM biocide from Halliburton Energy Services,
ity. By mixing Scleroglucan with clarified Xanthan, one still Inc., of Duncan, Okla., and a 2-bromo-2-nitro-1,3-pro
may be able to obtain the Superior temperature performance panediol commercially available under the tradename
of scleroglucanwhile also having the better regain permeabil BE-6TM biocide from Halliburton Energy Services, Inc., of
ity characteristics of the clarified Xanthans. Duncan, Okla. In one embodiment, the bactericides are
The gelling agents comprising clarified Xanthan may be present in the acidic treatment fluid in an amount in the range
present in an acidic treatment fluid of the present invention in of from about 0.001% to about 1.0% by weight of the acidic
an amount of from about 1 lb/Mgal to about 200 lb/Mgal. In treatment fluid. In certain embodiments, when bactericides
embodiments wherein the gelling agents comprising clarified 10 are used in the viscosified acidic fluids of the present inven
Xanthan further comprise Scleroglucan, one may include tion, they may be added to the acidic treatment fluid before the
about 1 lb/Mgal to about 200 lb/Mgal of scleroglucan. In an gelling agent is added.
acidic treatment fluid that comprises hydrochloric acid, one Examples of corrosion inhibitors that may be suitable for
may include about 1 to about 200 lb/Mgal of scleroglucan. In use include acetylenic alcohols, Mannich condensation prod
embodiments wherein the gelling agents comprising clarified 15 ucts (such as those formed by reacting an aldehyde, a carbo
Xanthan further comprise diutan, one may include about 1 to nyl containing compound and a nitrogen containing com
about 200 lb/Mgal of diutan. In an acidic treatment fluid that pound), unsaturated carbonyl compounds, unsaturated ether
comprises about 15% hydrochloric acid, one may include compounds, formamide, formic acid, formates, other sources
about 1 to about 200 lb/Mgal of diutan. In some embodi of carbonyl, iodides, terpenes, and aromatic hydrocarbons,
ments, one may include about 10 to about 150 lb/Mgal of coffee, tobacco, gelatin, cinnamaldehyde, cinnamaldehyde
clarified Xanthan, Scleroglucan, and/or diutan. A person of derivatives, acetylenic alcohols, fluorinated Surfactants, qua
skill in the art with the benefit of this disclosure will recognize ternary derivatives of heterocyclic nitrogen bases, quaternary
that any specific concentration or narrower range of concen derivatives of halomethylated aromatic compounds, forma
trations of the gelling agents of the present invention encom mides, combinations of such compounds used in conjunction
passed by the broader concentration ranges specifically 25 with iodine, quaternary ammonium compounds, and combi
articulated above may be used and/or may be particularly nations thereof. Corrosion inhibitors that may be suitable are
advantageous for a particular embodiment of the present available from Halliburton Energy Services and include:
invention. “MSA IITM corrosion inhibitor, “MSA IIITM corrosion
In certain embodiments, the acidic treatment fluids of the inhibitor, “HAI-404MTM acid corrosion inhibitor, “HAI
present invention also may comprise any additional additive 30 81 MTM Acid corrosion inhibitor, “HAI-85MTM Acid corro
that may be Suitable in a particular application of the present sion inhibitor, “HAI-202 Environmental Corrosion Inhibi
invention, including, but not limited to, any of the following: tor. “HAI-OS Corrosion Inhibitor, “HAI-GE Corrosion
hydrate inhibitors, clay stabilizers, bactericides, salt substi Inhibitor, and “FDP-S692-03 Corrosion inhibitor for
tutes (such as tetramethyl ammonium chloride), relative per organic acids. In certain embodiments, a corrosion inhibitor
meability modifiers (such as HPT-1TM chemical additive 35 activator may be included. Examples of corrosion inhibitor
available from Halliburton Energy Services, Duncan, Okla.), activators that may be used include, but are not limited to,
Sulfide Scavengers, fibers, nanoparticles, consolidating cuprous iodide; cuprous chloride; antimony compounds Such
agents (such as resins and/or tackifiers), corrosion inhibitors, as antimony oxides, antimony halides, antimony tartrate,
corrosion inhibitor intensifiers, pH control additives, surfac antimony citrate, alkali metal salts of antimony tartrate and
tants, breakers, fluid loss control additives, scale inhibitors, 40 antimony citrate, alkali metal salts of pyroantimonate and
asphaltene inhibitors, paraffin inhibitors, salts, bactericides, antimony adducts of ethylene glycol; bismuth compounds
crosslinkers, stabilizers, chelants, foamers, defoamers, emul such as bismuth oxides, bismuth halides, bismuth tartrate,
sifiers, demulsifiers, iron control agents, solvents, mutual bismuth citrate, alkali metal salts of bismuth tartrate and
Solvents, particulate diverters, gas phase, carbon dioxide, bismuth citrate; iodine; iodide compounds; formic acid; and
nitrogen, other biopolymers, synthetic polymers, friction 45 mixtures of the foregoing activators such as a mixture of
reducers, combinations thereof, or the like. The acidic treat formic acid and potassium iodide. Corrosion inhibitors inten
ment fluids of the present invention also may include other sifiers that may be suitable are available from Halliburton
additives that may be suitable for a given application, as will Energy Services and include: “HII-500TM Corrosion inhibi
be recognized by a person of ordinary skill in the art, with the tor intensifier, “HII-500MTM'Corrosion inhibitor intensifier,
benefit of this disclosure. 50 “HII-124B' Acid inhibitor intensifier, “HII-124CTM Inhibi
Examples of hydrate inhibitors that may be suitable for use tor intensifier, and “HII-124FTM corrosion inhibitor intensi
include thermodynamic inhibitors, methanol, mutual Sol fier. The amount of a corrosion inhibitor to include in an
vents, monoethylene glycol (MEG), di-ethylene glycol acidic treatment fluid of the present invention will depend on
(DEG), glycols, kinetic inhibitors, and anti-agglomerants. many factors, including but not limited to, the metallurgy the
Others known in the art may be suitable as well. 55 acid will contact, contact time, temperature, other acid blend
In some embodiments, the acidic treatment fluids of the additives, etc. Where included, the amount of a corrosion
present invention may contain bactericides, interalia, to pro inhibitor to include may range from about 0.1% to about 3%
tect both the subterranean formation as well as the viscosified by volume where liquid products are used and from about
treatment fluid from attack by bacteria. Such attacks may be 0.5% to about 200% by weight where solid products are used.
problematic because they may lower the viscosity of the 60 Suitable iron control agents are available from Halliburton
acidic treatment fluid, resulting in poorer performance. Such Energy Services and include: “FE-2TM Iron sequestering
as poorer sand Suspension properties, for example. Any bac agent, “FE-2ATM Buffering agent, “FE-3TM” Iron control
tericides known in the art are Suitable. An artisan of ordinary agent, “FE-3ATM Iron control agent, “FE-5ATM” Iron con
skill with the benefit of this disclosure will be able to identify trol agent, “FERCHEKR” Ferric iron inhibitor,
a suitable bactericide and the proper concentration of Such 65 “FERCHEKR A Reducing agent, and “FERCHEKR SC
bactericide for a given application. Examples of suitable bac Iron control system. Other Suitable iron control agents
tericides include, but are not limited to, a 2,2-dibromo-3- include those described in U.S. Pat. Nos. 6,315,045, 6,525,
 US 7,727,937 B2
11 12
011, 6,534,448, and 6,706,668, the relevant disclosures of Examples of acid generating compounds that may be suit
which are hereby incorporated by reference. able for use in the present invention include, but are not
In some embodiments, a pH control additive may be limited to, esters, aliphatic polyesters, ortho esters, which
included, which may compriseachelating agent. When added may also be known as ortho ethers, poly (ortho esters), which
to the treatment fluids of the present invention, such a chelat 5 may also be known as poly(ortho ethers), poly(lactides), poly
ing agent, among other functions, may chelate any dissolved (glycolides), poly(e-caprolactones), poly(hydroxybutyrates),
iron (or other divalent or trivalent cation) that may be present poly(anhydrides), or copolymers thereof. Derivatives and
in the water. Such chelating may prevent Such ions from combinations also may be suitable. The term “copolymeras
crosslinking the gelling agent molecules. Such crosslinking used herein is not limited to the combination of two polymers,
may be problematic, interalia, because it may cause severe 10 but includes any combination of polymers, e.g., terpolymers
filtration problems, prevent injection in to the formation to and the like. Other suitable acid-generating compounds
optimize iron control, and/or cause polymer break or the include: esters including, but not limited to, ethylene glycol
formation of residue in the formation. Any Suitable chelating monoformate, ethylene glycol diformate, diethylene glycol
agent may be used with the present invention. Examples of diformate, glyceryl monoformate, glyceryl diformate, glyc
chelating agents that may be Suitable include, but are not 15 eryl triformate, triethylene glycol diformate and formate
limited to, an anhydrous form of citric acid, commercially esters of pentaerythritol. An example of a suitable acid gen
available under the tradename “FE-2TM Iron Sequestering erating compound is a citrate ester commercially available
Agent from Halliburton Energy Services, Inc., of Duncan, from Halliburton Energy Services, Inc., of Duncan, Okla.,
Okla. Another example of a suitable chelating agent is a under the tradename MATRIXFLOTM II Breaker. Other Suit
Solution of citric acid dissolved in water, commercially avail able materials may be disclosed in U.S. Pat. Nos. 6,877.563
able under the tradename “FE-2ATM buffering agent from and 7,021,383, the disclosures of which are incorporated by
Halliburton Energy Services, Inc., of Duncan, Okla. Another reference.
example of a Suitable chelating agent is sodium citrate from The optional pH control additive also may comprise a base
Halliburton Energy Services, Inc. of Duncan, Okla. Other to elevate the pH of the treatment fluid, for example, when this
chelating agents that may be suitable for use with the present 25 fluid is used as a diverting fluid. Any known base that is
invention include, interalia, nitrilotriacetic acid and any form compatible with the gelling agents comprising clarified Xan
of ethylene diamine tetracetic acid ("EDTA) or its salts, than can be used in the viscosified treatment fluids of the
hydroxyethylethylenediaminetriacetic acid (“HEDTA), present invention. Examples of bases that may be suitable
dicarboxymethyl glutamic acid tetrasodium salt (“GLDA), include, but are not limited to, Sodium hydroxide, potassium
diethylenetriaminepentaacetic acid (“DTPA), propylenedi 30 carbonate, potassium hydroxide, Sodium bicarbonate,
aminetetraacetic acid (“PDTA), ethylenediaminedi(o-hy Sodium carbonate, derivatives thereof, and combinations
droxyphenylacetic) acid (“EDDHA), glucoheptonic acid, thereof. An example of a base that may be suitable is a
gluconic acid, sodium citrate, phosphonic acid, salts thereof, solution of 25% sodium hydroxide commercially available
and the like. In some embodiments, the chelating agent may from Halliburton Energy Services, Inc., of Duncan, Okla.,
be a sodium or potassium salt. Generally, the chelating agent 35 under the tradename “MO-67TM pH control agent. An
may be present in an amount Sufficient to prevent crosslinking example of a base solution that may be suitable is a solution
of the gelling agent molecules by any free iron (or any other of potassium carbonate commercially available from Halli
divalent or trivalent cation) that may be present. In one burton Energy Services, Inc., of Duncan, Okla., under the
embodiment, the chelating agent may be present in an amount tradename “BA-40LTM buffering agent. One of ordinary
offrom about 0.02% to about 2.0% by weight of the treatment 40 skill in the art with the benefit of this disclosure will recognize
fluid. In another embodiment, the chelating agent is present in the suitable bases that may be used to achieve a desired pH
an amount in the range of from about 0.02% to about 0.5% by elevation in a particular application of the present invention.
weight of the treatment fluid. One of ordinary skill in the art In still another embodiment, the optional pH control addi
with the benefit of this disclosure will be able to determine the tive may comprise a combination of an acid and a chelating
proper concentration of optional chelating agents for a par 45 agent or a base and a chelating agent. Such combinations may
ticular application. be suitable, interalia, when the addition of a chelating agent
In another embodiment, the optional pH control additive (e.g., in an amount Sufficient to chelate the iron present) is
may be an acid, which may comprise any known acid, includ insufficient by itself to achieve the desired pH level.
ing but not limited to the acid already included in the acidic In some embodiments, the acidic treatment fluids of the
treatment fluids of the present invention. Examples of acids 50 present invention may include Surfactants, e.g., to improve
that may be suitable include, inter alia, hydrochloric acid, the compatibility of the acidic treatment fluids with other
hydrofluoric acid, phosphonic acid, p-toluenesulfonic acid, fluids (like any formation fluids) that may be present in the
acetic acid, formic acid, citric acid, derivatives thereof, and subterranean formation. A person of ordinary skill, with the
combinations thereof. benefit of this disclosure, will be able to identify the type of
In some embodiments, the pH control additive may be an 55 Surfactant as well as the appropriate concentration of Surfac
acid composition. Examples of Suitable acid compositions tant to be used. Examples of surfactants that may be suitable
may comprise an acid, an acid generating compound, and include, but are not limited to, ethoxylated nonyl phenol
combinations thereof. Any known acid may be suitable for phosphate esters, nonionic Surfactants, cationic Surfactants,
use with the treatment fluids of the present invention. anionic Surfactants, amphoteric/Zwitterionic Surfactants,
Examples of acids that may be suitable for use in the present 60 alkyl phosphonate Surfactants, linear alcohols, nonylphenol
invention include, but are not limited to organic acids (e.g., compounds, alkyoxylated fatty acids, alkylphenol alkoxy
formic acids, acetic acids, carbonic acids, citric acids, gly lates, ethoxylated amides, ethoxylated alkylamines, betaines,
colic acids, lactic acids, ethylenediaminetetraacetic acid methyl ester sulfonates (e.g., as described in U.S. Patent
(“EDTA), hydroxyethyl ethylenediamine triacetic acid Application Nos. 2006/0180310, 2006/0180309, 2006/
(“HEDTA), and the like), inorganic acids (e.g., hydrochloric 65 0183646 and U.S. Pat. No. 7,159,659, the relevant disclosures
acid, hydrofluoric acid, phosphonic acid, p-toluenesulfonic of which are incorporated herein by reference), hydrolyzed
acid, and the like), and combinations thereof. keratin (e.g., as described in U.S. Pat. No. 6,547.871, the
 US 7,727,937 B2
13 14
relevant disclosure of which is incorporated herein by refer embodiments where it is desirable to foam the treatment
ence), SulfoSuccinates, taurates, amine oxides, alkoxylated fluids of the present invention, Surfactants such as
fatty acids, alkoxylated alcohols (e.g., lauryl alcohol ethoxy HY-CLEAN (HC-2)TM surface-active suspending agent or
late, ethoxylated nonyl phenol), ethoxylated fatty amines, AQF-2TM additive, both commercially available from Halli
ethoxylated alkyl amines (e.g., cocoalkylamine ethoxylate), burton Energy Services, Inc., of Duncan, Okla., may be used.
betaines, modified betaines, alkylamidobetaines (e.g., cocoa Additional examples of foaming agents that may be utilized
midopropyl betaine), quaternary ammonium compounds to foam and stabilize the treatment fluids of this invention
(e.g., trimethyltallowammonium chloride, trimethylcocoam include, but are not limited to, betaines, amine oxides, methyl
monium chloride), derivatives thereof, and mixtures thereof. ester Sulfonates, alkylamidobetaines such as cocoamidopro
Suitable surfactants may be used in a liquid or powder form. 10 pyl betaine, alpha-olefin Sulfonate, trimethyltallowammo
Where used, the surfactants are present in the acidic treatment nium chloride, C8 to C22 alkylethoxylate sulfate and trim
fluid in an amount sufficient to prevent incompatibility with ethylcocoammonium chloride. Other suitable surfactants that
formation fluids or well bore fluids. In an embodiment where may or may not be foamers in a particular application that are
liquid Surfactants are used, the Surfactants may be present in available from Halliburton Energy Services include: 19N,
an amount in the range of from about 0.01% to about 5.0% by 15 G-SPERSE dispersant, HOWCO-SUDSTM foaming agent,
Volume of the acidic treatment fluid. In one embodiment, the and A-SPERSETM dispersing aid for acid additives. Other
liquid Surfactants are present in an amount in the range of Suitable foaming agents and foam stabilizing agents may be
from about 0.01% to about 2.0% by volume of the acidic included as well, which will be known to those skilled in the
treatment fluid. In embodiments where powdered surfactants art with the benefit of this disclosure.
are used, the Surfactants may be present in an amount in the While typically not required, the acidic treatment fluids of
range of from about 0.001% to about 0.5% by weight of the the present invention also may comprise breakers capable of
acidic treatment fluid. Examples of surfactants that may be reducing the viscosity of the acidic treatment fluid at a desired
suitable include non-emulsifiers commercially available time. Examples of such breakers that may be suitable for the
from Halliburton Energy Services, Inc., of Duncan, Okla., acidic treatment fluids of the present invention include, but
under the tradenames “LOSURF-300MTM nonionic Surfac 25 are not limited to, Sodium chlorite, hypochlorites, perborates,
tant, “LOSURF-357TM nonionic surfactant, “LOSURF persulfates, peroxides (including organic peroxides),
400TM surfactant, “LOSURF-2000STM solid surfactant, enzymes, derivatives thereof, and combinations thereof.
“LOSURF-2000MTM solid surfactant, and “LOSURF Other suitable breakers may include suitable acids. Examples
259TM nonionic non-emulsifier. Another example of a sur of peroxides that may be suitable include tert-butyl hydrop
factant that may be Suitable is a non-emulsifier commercially 30 eroxide and tert-amyl hydroperoxide. A breaker may be
available from Halliburton Energy Services, Inc., of Duncan, included in an acidic treatment fluid of the present invention
Okla., under the tradename “NEA-96MTM Surfactant. Other in an amount and form sufficient to achieve the desired vis
examples of surfactants that may be suitable that are commer cosity reduction at a desired time. The breaker may be for
cially available from Halliburton Energy Services in Duncan, mulated to provide a delayed break, if desired. For example,
Okla. are products “SGA-1.” “EFS-1,” “EFS-2.” “EFS-3.” 35 a suitable breaker may be encapsulated if desired. Suitable
and “EFS-4. Other surfactants that may be suitable may encapsulation methods are known to those skilled in the art.
include betaines and quaternary ammonium compounds. One suitable encapsulation method that may be used involves
Examples of betaines that are commercially available include coating the breaker(s) with a material that will degrade when
MIRATAINER) and MIRATAINER BET 0-30 both available placed downhole so as to release the breaker at the appropri
for Rhodia and REWOTERICOR AM TEG available for 40 ate time. Coating materials that may be suitable include, but
Degussa. Examples of commercially available quaternary are not limited to, polymeric materials that will degrade when
ammonium compounds include ARQUADR. 22-80 and downhole. The terms “degrade.” “degradation,” or “degrad
ETHOQUADR) O/12 PG both available from Akzo Nobel able” refer to both the two relatively extreme cases of hydro
and GENAMIN KDMP available from Clariant. It may be lytic degradation that the degradable material may undergo,
beneficial to add a surfactant to an acidic treatment fluid of the 45 i.e., heterogeneous (or bulk erosion) and homogeneous (or
present invention as that fluid is being pumped downhole, Surface erosion), and any stage of degradation in between
among other things, to help reduce the possibility of forming these two. This degradation can be a result of inter alia, a
emulsions with the formation crude oil. Furthermore, in some chemical or thermal reaction or a reaction induced by radia
embodiments, microemulsion additives optionally may be tion. Suitable examples of materials that can undergo Such
included in the treatment fluids of the present invention. 50 degradation include polysaccharides such as dextran or cel
Examples of microemulsion additives that may be suitable lulose; chitins; chitosans; proteins; aliphatic polyesters; poly
include, but are not limited to, “PEN-88MTM surfactant, (lactides); poly(glycolides); poly(e-caprolactones); poly(hy
“PEN-88HTTM surfactant, “SSO-21E surfactant, “SSO droxybutyrates); poly(anhydrides); aliphatic polycarbonates;
21 MWTM surfactant, GASPERM 1000TM Microemulsion orthoesters, poly(orthoesters); poly(amino acids); poly(eth
Surfactant/Solvent Additive, which are all commercially 55 ylene oxides); polyphosphaZenes; derivatives thereof, and
available from Halliburton Energy Services, Inc., of Duncan, combinations thereof. Ifused, a breaker should be included in
Okla. Other microemulsion additives that may be suitable are a composition of the present invention in an amount Sufficient
MA-845 additive and MA-844 additive, commercially avail to facilitate the desired reduction in viscosity in a viscosified
able from CESI Chemical of Duncan, Okla.; SHALESURF treatment fluid. For instance, peroxide concentrations that
1000 additive, commercially available from Frac Tech Ser 60 may be used vary from about 0.1 to about 10 gallons of
vices of Aledo, Tex.; and those disclosed in U.S. Patent App. peroxide per 1000 gallons of the acidic treatment fluid.
No. 2003/0166472, the relevant disclosure of which is incor Optionally, an acidic treatment fluid of the present inven
porated by reference. tion may contain an activator or a retarder, inter alia, to
It should be noted that, in some embodiments, it may be optimize the rate at which the fluid is “broken' (i.e., the
beneficial to add a surfactant to a treatment fluid of the present 65 viscosity of the fluid is reduced). Any known activator or
invention as that fluid is being pumped downhole to help retarder that is compatible with the fluid and the components
eliminate the possibility of foaming. However, in those thereof is suitable for use in the present invention. Examples
 US 7,727,937 B2
15 16
of such activators that may be suitable include, but are not amounts of scale inhibitors that may be included in the treat
limited to, acid generating materials, chelated iron, copper, ment fluids of the present invention may range from about
cobalt, reducing Sugars, derivatives thereof, and combina 0.05 to 100 gallons per about 1000 gallons of the treatment
tions thereof. Examples of retarders that may be suitable fluid.
include Sodium thiosulfate and diethylene triamine. In some Salts optionally may be included in the acidic treatment
embodiments, the Sodium thiosulfate may be used in a range fluids of the present invention for many purposes, including
of from about 1 to about 100 lbs per 1000 gallons of acidic adjusting the density of the fluid. One of ordinary skill in the
treatment fluid. A preferred concentration range may be from art with the benefit of this disclosure will recognize the par
about 5 to about 20 lbs per 1000 gallons. A person of ordinary ticular type of salt appropriate for particular application,
skill with the benefit of this disclosure will be able to identify 10 given considerations such as protection of the formation, the
a suitable activator or retarder and the proper concentration of presence or absence of reactive clays in the formation adja
Such activator or retarder for a given application. cent to the well bore, compatibility with the other acidic
The acidic treatment fluids of the present invention also treatment fluid additives, and the factors affecting wellhead
may comprise Suitable fluid loss control agents. Such fluid control. To determine whether a salt may be used, a compat
loss control agents may be useful, among other instances, 15 ibility test may be performed to identify potential compatibil
when an acidic treatment fluid of the present invention is ity problems. From such tests, one of ordinary skill in the art
being used in a fracturing application. This may be due, in with the benefit of this disclosure will be able to determine
part, to the clarified xanthan's potential to leak off into for whether a salt should be included in an acidic treatment fluid
mation. Any fluid loss agent that is compatible with the treat of the present invention, as well as the appropriate selection of
ment fluid may be suitable for use in the present invention. salts. Suitable salts may include, but are not limited to, cal
Examples include, but are not limited to, starches, silica flour, cium bromide, Zinc bromide, calcium chloride, sodium chlo
and diesel dispersed in a fluid. Other examples of fluid loss ride, sodium bromide, potassium bromide, potassium chlo
control additives that may be suitable are those that comprise ride, Sodium nitrate, Sodium formate, potassium formate,
a degradable material. Suitable degradable materials include cesium formate, magnesium chloride, ammonium chloride,
degradable polymers. Specific examples of suitable polymers 25 derivatives thereof, mixtures thereof, and the like.
include polysaccharides such as dextran or cellulose; chitins: The treatment fluids of the present invention optionally
chitosans; proteins; aliphatic polyesters; poly(lactides); poly may comprise a suitable crosslinker, inter alia, to crosslink
(glycolides); poly(glycolide-co-lactides); poly(e-caprolac the clarified Xanthan. Crosslinking may be desirable at higher
tones); poly(3-hydroxybutyrates); poly(3-hydroxybutyrate temperatures and/or when the sand Suspension properties of a
co-hydroxyvalerates); poly(anhydrides); aliphatic poly 30 particular fluid of the present invention may need to be altered
(carbonates); poly(orthoesters); poly(amino acids); poly for a particular purpose. Suitable crosslinkers include, but are
(ethylene oxides); poly(phosphazenes); derivatives thereof; not limited to, boron derivatives; potassium derivatives,
or combinations thereof. If included, a fluid loss additive including but not limited to, potassium periodate or potas
should be added to an acidic treatment fluid of the present sium iodate; ferric iron derivatives; magnesium derivatives;
invention in an amount of about 5 to about 2000 pounds per 35 and the like. Any crosslinker that is compatible with the
1000 gallons of the acidic treatment fluid. In certain embodi clarified Xanthan in the gelling agent may be suitable for use
ments, the fluid loss additive may be included in an amount in the present invention. One of ordinary skill in the art, with
from about 10 to about 50 pounds per 1000 gallons of the the benefit of this disclosure, will recognize when such
acidic treatment fluid. For some liquid additives like diesel, crosslinkers are appropriate and what particular crosslinker
these may be included in an amount from about 0.01% to 40 will be most Suitable. Typically, a crosslinking agent may be
about 20% by volume; in some embodiments, these may be included in an amount of from about 0.01 lb/Mgal to about 15
included in an amount from about 1% to about 10% by vol 1b/Mgal.
le. The treatment fluids of the present invention optionally
Scale inhibitors optionally may be added to the acidic may comprise a stabilizer, for example, if a chosen acidic
treatment fluids of the present invention, for example, when 45 treatment fluid of the present invention is experiencing a
an acidic treatment fluid of the present invention is not par Viscosity degradation. One example of a situation where a
ticularly compatible with the formation waters in the forma stabilizer might be beneficial is where the borehole tempera
tion in which it is being used. Any scale inhibitor that is ture of the well bore is sufficient by itself to break the acidic
compatible with the acidic treatment fluid in which it will be treatment fluid. Suitable stabilizers may include, but are not
used may be suitable for use in the present invention. This 50 limited to, sodium thiosulfate. Such stabilizers may be useful,
may include water Soluble organic molecules with carboxylic for example, when the acidic treatment fluids of the present
acid, aspartic acid, maleic acids, Sulphonic acids, phosphonic invention are utilized in a Subterranean formation having a
acid and phosphate esters groups including copolymers, ter temperature above about 150°F. If included, a stabilizer may
polymers, grafted copolymers, derivatives thereof, and com be added in an amount from about 1 lb to about 50 lb per 1000
binations thereof. Examples of Such compounds include ali 55 gal of acidic treatment fluid. In other embodiments, a stabi
phatic phosphonic acids such as diethylene triamine penta lizer may be included in an amount of from about 5 to about
(methylene phosphonate) and polymeric species such as 20 lb per 1000 gal of acidic treatment fluid.
polyvinylsulphonate. The scale inhibitor may be in the form In certain embodiments, an acidic treatment fluid of the
of the free acid, or may be in the form of mono- and polyvalent present invention may be prepared according to a process
cation salts such as those comprising Na', K", Al, Fe, Ca", 60 comprising: providing an aqueous base fluid having a suitable
Mg", NH," cations. An example of a preferred scale inhibitor density; adding optional additives such as biocides, chelating
is “SCALECHECKOR) LP-55 Scale Inhibitor’ from Hallibur agents, pH control agents, and the like; filtering the aqueous
ton Energy Services in Duncan, Okla. Another example of a base fluid through a 2-um (or finer) filter, dispersing the
preferred scale inhibitor is “LP-65TM Scale Inhibitor” avail gelling agent comprising a clarified Xanthan into the aqueous
able from Halliburton Energy Services in Duncan, Okla. If 65 base fluid with adequate shear to fully disperse polymer
used, a scale inhibitor should be included in an amount effec therein; and mixing the treatment fluid until the clarified
tive to inhibit scale formation. For some applications, suitable xanthan is fully hydrated. However, these methods may be
 US 7,727,937 B2
17 18
varied in any manner appropriate for a particular application and the time averaged. The results are shown in FIG. 1. In
of the present invention, as will be recognized by a person of FIG. 1, the apparent viscosity is given on the majorY-axis and
skill in the art, with the benefit of this disclosure. the sample temperature is given on the minor Y-axis. These
An embodiment of the present invention provides a method data demonstrate the certain treatment fluids of the present
comprising: providing an acidic treatment fluid that com invention comprising a gelling agent that comprises clarified
prises an aqueous base fluid, an acid, and a gelling agent that Xanthan can maintain higher viscosities at higher tempera
comprises clarified Xanthan; and introducing the acidic treat tures than certain similar fluids comprising a standard Xan
ment fluid into a portion of a Subterranean formation. than gelling agent.
An embodiment of the present invention provides a method
of acidizing a portion of a Subterranean formation compris 10 Example 2
ing: providing an acidic treatment fluid that comprises an
aqueous base fluid, an acid, and agelling agent that comprises Fluid preparation: Five acidic treatment fluids were pre
clarified Xanthan; contacting a portion of the Subterranean pared by mixing a 15% HCl fluid containing varying ratios of
formation with the acidic treatment fluid; and allowing the clarified xanthan and/or scleroglucan at 83.47 lb/Mgal in a
acidic treatment fluid to interact with a component of the 15 Waring blender. The fluid was mixed (hydrated) for 30 min
Subterranean formation so that at least a portion of the com utes. Acidic treatment fluids comprising a Scleroglucan gel
ponent is dissolved. ling agent and various compositions of a clarified Xanthan and
An embodiment of the present invention provides a method Scleroglucan gelling agent were prepared in a similar manner
of diverting fluids in a Subterranean formation. In an example using 83.47 lb/Mgal. Table 1 shows the ratio of clarified
of Such a method, the method may comprise: providing an Xanthan and Scleroglucan of each sample fluid tested.
acidic treatment fluid comprising an aqueous base fluid, an
acid, and a gelling agent that comprises clarified Xanthan; TABLE 1
introducing the acidic treatment fluid into a well bore that
penetrates the Subterranean formation; and allowing at least a Sample Fluids Tested.
first portion of the acidic treatment fluid to penetrate into a 25
Sample Composition No. Clarified Xanthan (%) Scleroglucan (%)
portion of the Subterranean formation so as to Substantially
divert a second portion of the acidic treatment fluid or another 1
2
1OO
O
O
1OO
treatment fluid to another portion of the subterranean forma 3 75 25
tion. In certain embodiments, the first portion of the acidic 4 50 50
may divert the second portion of the acidic treatment fluid or 30 5 25 75
another treatment fluid to another portion of the subterranean
formation by becoming a sufficiently rigid gel to do so. These
steps may be repeated as desired. Fluid evaluation: The fluids were evaluated on a Nordman
Furthermore, the acidic treatment fluids used in the meth Model 50 viscometer using a standard bob spring and the BI
ods of the present invention (or any component thereof) may 35 bob. Testing protocol was a modified API2 test with 1 F/min
be provided “on-the-fly” (i.e., at a jobsite just prior to use, temperature ramp. The results are shown in FIG. 2. In FIG. 2,
with or without a hydration tank) or by batch process (pre the apparent viscosity is given on the major Y-axis and the
mixing). Additionally, the polymers of the present invention sample temperature is given on the minor Y-axis. FIG. 2
may be used as a dry powder, an liquidgel concentrate (LGC), demonstrates that certain treatment fluids of the present
a paste, or as a slurry. 40 invention comprising a gelling agent that comprises clarified
To facilitate a better understanding of the present inven Xanthan and Scleroglucan may exhibit improved rheological
tion, the following examples of some embodiments are given. performance as compared to a treatment fluid of the present
In no way should such examples be read to limit, or define, the invention wherein the gelling agent comprises clarified Xan
Scope of the invention. than alone.
45 Therefore, the present invention is well adapted to attain
EXAMPLES the ends and advantages mentioned as well as those that are
inherent therein. The particular embodiments disclosed
Example 1 above are illustrative only, as the present invention may be
modified and practiced in different but equivalent manners
Fluid preparation: Acidic treatment fluids comprising Xan 50 apparent to those skilled in the art having the benefit of the
than were prepared by making a 15% HCl Solution containing teachings herein. Furthermore, no limitations are intended to
83.47 lb/Mgal of standard Xanthan commercially available the details of construction or design herein shown, other than
from Halliburton Energy Services, Duncan Okla. under the as described in the claims below. It is therefore evident that
tradename “WG-24' in a Waring blender. The fluid was the particular illustrative embodiments disclosed above may
mixed (hydrated) for 30 minutes. Acidic treatment fluids 55 be altered or modified and all such variations are considered
comprising a clarified Xanthangelling agent were prepared in within the scope and spirit of the present invention. In par
a similar manner using 83.47 lb/Mgal of a clarified xanthan ticular, every range of values (of the form, “from about a to
instead of the standard Xanthan. about b,” or, equivalently, “from approximately a to b,” or,
Fluid evaluation: The fluids were then evaluated on a Nor equivalently, “from approximately a-b') disclosed herein is
dman Model 50 viscometer using a modified API2 program 60 to be understood as referring to the power set (the set of all
that consisted of 118/29/88 rpm ramping scan with 88 rpm as subsets) of the respective range of values, and set forth every
the base. When the sample reached the target temperature, it range encompassed within the broader range of values. More
performed its first ramping Scan. Thereafter, ramping scans over, the indefinite articles“a” and “an', as used in the claims,
occurred every 10 to 15 minutes. Each ramping scan provided is defined hereinto mean one or more than one of the element
shears at 118 rpm (100), 88 rpm (75), 59 rpm (50), and 65 that it introduces. Also, the terms in the claims have their
29 rpm (25'), then back to 59, 88, and 118 rpm before plain, ordinary meaning unless otherwise explicitly and
settling to 88 rpm. At the end of the test, the data was collected clearly defined by the patentee.
 US 7,727,937 B2
19 20
What is claimed is: 11. The acidic treatment fluid of claim 10 wherein the acid
1. An acidic treatment fluid that comprises an aqueous base comprises at least one acid selected from the group consisting
fluid, an acid, and a gelling agent comprising clarified Xan of hydrochloric acid; hydrofluoric acid; acetic acid; formic
than. acid; citric acid; lactic acid; glycolic acid; Sulfamic acid; any
2. The acidic treatment fluid of claim 1 wherein the pH of 5 derivative thereof; and any combination thereof
the acidic treatment fluid is about 4 or less. 12. The acidic treatment fluid of claim 10 wherein the
3. The acidic treatment fluid of claim 1 wherein the acid gelling agent is present in the acidic treatment fluid in an
comprises at least one acid selected from the group consisting amount of about 1 lb/Mgal to about 200 lb/Mgal.
of hydrochloric acid; hydrofluoric acid; acetic acid; formic 13. The acidic treatment fluid of claim 10 wherein the
acid; citric acid; lactic acid; glycolic acid; Sulfamic acid; any 10 gelling agent is at least partially crosslinked through a
derivative thereof; and any combination thereof. crosslinking reaction that comprises a crosslinking agent.
4. The acidic treatment fluid of claim 1 wherein the gelling 14. The acidic treatment fluid of claim 10 further compris
agent is present in the acidic treatment fluid in an amount of ing diutan.
about 11b/Mgal to about 200 lb/Mgal. 15. The acidic treatment fluid of claim 10 further compris
5. The acidic treatment fluid of claim 1 wherein the gelling 15
ing a gas in an amount of about 5% to about 95% by volume.
agent is at least partially crosslinked through a crosslinking 16. The acidic treatment fluid of claim 10 wherein the
reaction that comprises a crosslinking agent. clarified Xanthan comprises a Xanthan that has a flow rate of at
6. The acidic treatment fluid of claim 1 further comprising least about 200 ml in 2 minutes at ambient temperature in a
at least one additive selected from the group consisting of a filtering laboratory test on a Baroid Filter Press using 40 psi of
hydrate inhibitor; a corrosion inhibitor; a pH control additive: differential pressure and a 9 cm Whatman filter paper having
a Surfactant; a salt; a breaker, a fluid loss control additive; a a 2.7L pore size.
scale inhibitor; an asphaltene inhibitor; a paraffin inhibitor; a 17. A subterranean well treatment system comprising an
bactericide; a crosslinker, a stabilizer, a chelant; a foaming aqueous base fluid, an acid, and agelling agent that comprises
agent; a defoamer, an emulsifier; a demulsifier, an iron con clarified Xanthan.
trol agent; a solvent; a mutual solvent; a particulate diverter, 25
a gas; carbon dioxide; nitrogen; a biopolymer; a synthetic 18. The subterranean well treatment system of claim 17
polymer; a friction reducer, an activator; a retarder; and any wherein the acid comprises at least one acid selected from the
combination thereof. group consisting of hydrochloric acid; hydrofluoric acid;
7. The acidic treatment fluid of claim 1 further comprising acetic acid; formic acid; citric acid; lactic acid; glycolic acid;
at least one additional biopolymer selected from the group 30 Sulfamic acid; any derivative thereof, and any combination
consisting of Scleroglucan, diutan, any derivative thereof, thereof
any clarified version thereof, and any combination thereof. 19. The subterranean well treatment system of claim 17
8. The acidic treatment fluid of claim 1 wherein the acidic further comprising at least one additional biopolymer
treatment fluid comprises a gas in an amount of about 5% to selected from the group consisting of Scleroglucan, diutan,
about 95% by volume of the acidic treatment fluid. 35 any derivative thereof, any clarified version thereof, and any
9. The acidic treatment fluid of claim 1 wherein the clari combination thereof.
fied Xanthan comprises a Xanthan that has a flow rate of at 20. The subterranean well treatment system of claim 17
least about 200 ml in 2 minutes at ambient temperature in a wherein the clarified Xanthan comprises a Xanthan that has a
filtering laboratory test on a Baroid Filter Press using 40 psi of flow rate of at least about 200 ml in 2 minutes at ambient
differential pressure and a 9 cm Whatman filter paper having 40 temperature in a filtering laboratory test on a Baroid Filter
a 2.7L pore size. Press using 40 psi of differential pressure and a 9 cm What
10. An acidic treatment fluid that comprises an aqueous man filter paper having a 2.7L pore size.
base fluid, an acid, and a gelling agent comprising clarified
Xanthan and Scleroglucan. k k k k k