WO2000005322A1 - Polysaccharide-containing well drilling and servicing fluids - Google Patents

Polysaccharide-containing well drilling and servicing fluids Download PDF

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Publication number
WO2000005322A1
WO2000005322A1 PCT/US1999/010047 US9910047W WO0005322A1 WO 2000005322 A1 WO2000005322 A1 WO 2000005322A1 US 9910047 W US9910047 W US 9910047W WO 0005322 A1 WO0005322 A1 WO 0005322A1
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WO
WIPO (PCT)
Prior art keywords
fluid
oligosaccharide mixture
fluids
aqueous
polysaccharide
Prior art date
Application number
PCT/US1999/010047
Other languages
French (fr)
Inventor
Roy F. House
Original Assignee
Venture Innovations, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Venture Innovations, Inc. filed Critical Venture Innovations, Inc.
Priority to EA200100181A priority Critical patent/EA002815B1/en
Priority to CA002338444A priority patent/CA2338444C/en
Priority to AU38903/99A priority patent/AU3890399A/en
Priority to DE69922670T priority patent/DE69922670D1/en
Priority to EP99921783A priority patent/EP1114115B1/en
Priority to MXPA01000839A priority patent/MXPA01000839A/en
Priority to AT99921783T priority patent/ATE284936T1/en
Priority to BRPI9912417-3A priority patent/BR9912417B1/en
Publication of WO2000005322A1 publication Critical patent/WO2000005322A1/en
Priority to NO20010384A priority patent/NO330308B1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/04Aqueous well-drilling compositions
    • C09K8/06Clay-free compositions
    • C09K8/08Clay-free compositions containing natural organic compounds, e.g. polysaccharides, or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/04Aqueous well-drilling compositions
    • C09K8/14Clay-containing compositions
    • C09K8/18Clay-containing compositions characterised by the organic compounds
    • C09K8/20Natural organic compounds or derivatives thereof, e.g. polysaccharides or lignin derivatives
    • C09K8/206Derivatives of other natural products, e.g. cellulose, starch, sugars
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/04Aqueous well-drilling compositions
    • C09K8/26Oil-in-water emulsions
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/04Aqueous well-drilling compositions
    • C09K8/26Oil-in-water emulsions
    • C09K8/28Oil-in-water emulsions containing organic additives

Definitions

  • the invention relates to fluids used in the drilling and/or servicing of oil and/or gas wells, and particularly drilling fluids, drill-in fluids, workover fluids,
  • Such fluids are characterized as having a rheological profile which is shear
  • U.S. Patent No. 4.485.020 discloses the preparation of a
  • thermostable, viscous xanthan gum solution by heating a xanthan gum solution in
  • U.S. Patent No. 4.900.457 discloses that the thermal stability of aqueous polysaccharide solutions can be significantly enhanced by incorporating certain formate salts therein.
  • aqueous fluids particularly at low concentrations of soluble salts dissolved therein.
  • ELSRV fluids containing aqueous fluids which exhibit an enhanced low shear rate viscosity, which may hereinafter be referred to as ELSRV fluids, is enhanced, and the fluid loss is reduced, by adding to the ELSRV fluid an oligosaccharide mixture
  • the oligosaccharide mixture preferably consisting of the water soluble portion of thermally hydrolyzed lignocellulose.
  • the ELSRV fluids have a shear thinning index of at least 10,
  • thinning characteristics of the fluid preferably at least 20.
  • the oligosaccharide mixture also enhances the thermal stability of
  • shear rate viscosity such as fluids containing cellulose derivatives. It is an object of this invention to provide a process for enhancing the thermal stability of aqueous polysaccharide-containing fluids as evidenced by the low shear
  • compositions can comprise, consist essentially of, or consist of the stated
  • the method can comprise, consist essentially of, or consist of the stated
  • the oligosaccharide mixture (hereinafter sometimes referred to as "OSM")
  • the thermal hydrolysis may be carried out in any one of
  • the OSM may also be obtained by acid hydrolysis of lignocelluloses as well as by saccharification of wood.
  • the thermal hydrolysis is carried out by charging wood chips to a closed chamber (e.g.,
  • water solubles can be concentrated or rendered solid by removing w ater therefrom,
  • Water solubles resulting from such hydrolysis of lignocellulose materials as a class are applicable to this invention.
  • OSM of this invention made from pine wood is as follows: hexosans and
  • pentosans 70% by weight; lignin, 15% by weight: non-sugar carbohydrates, 10% by weight; and gums, 5% by weight.
  • the constituents of the OSM will vary somewhat depending on the type of lignocellulose material hydrolyzed and the
  • the constituents of the OSM can vary roughly as follows: pentosans and hexosans, 60-80%) by weight; lignin, 5-25% by weight; non-sugar
  • hexosans contain primarily from one to about four combined sugar units composed of arabinose, mannose, galactose, glucose, and xylose sugar units.
  • Patent No. 2,713,030 that the addition of small amounts of the OSM to clay-water drilling mud systems, such as from about 0.07-1.75 pounds of OSM per 42 gallon
  • low shear rate viscosity i.e., the viscosity at less than about one sec " 1 .
  • the minimum concentration of the OSM incorporated into the aqueous polysaccharide-containing fluids is that amount, as determined by routine testing,
  • the thermal stability can be determined by evaluating other properties of the fluids such as the viscosity at higher shear rates, fluid loss, and the like, and comparing the results
  • the concentration of the OSM will be from about 0.7 kg/m 3 (0.25
  • the polymers useful in the ELSRV fluids of this invention comprise any water soluble polymer which increases the low shear rate viscosity of the fluid to produce
  • biopolymers produced by the action of bacteria, fungi, or other microorganisms on a suitable substrate.
  • exemplary biopolymers are the polysaccharides produced
  • Patent No. 4,758,356 each incorporated herein by reference.
  • Other biopolymers useful in the fluids of this invention are the so-called welan gums produced by fermentation with a microorganism of the genus Alcaligenes. See for example
  • Scleroglucan polysaccharides produced by fungi of the genus sclerotium are Scleroglucan polysaccharides produced by fungi of the genus sclerotium.
  • polysaccharides are produced by cultivating a slime-forming species of Pesudomonas, Rhizobium, Alcaligenes or Agrobacterium, e.g., Pseudoraonas sp.
  • NCIB 11264 Pseudomonas sp. NCIB 11592 or Agrobacterium radiobacter NCIB
  • succinoglycan biopolymer is sold by Shell
  • cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl
  • polysaccharides as are well known in the art.
  • Such polysaccharides may increase the viscosity at higher shear rates, decrease the fluid loss, or provide other characteristics to the fluids.
  • the minimum concentration of the polymer required to increase the low shear rate viscosity of the fluid can be determined by routine testing.
  • concentration will be an amount sufficient to impart to the fluid the desired low shear rate viscosity. Generally the fluids will contain a concentration from about
  • the water base borehole fluids of this invention generally will contain
  • the fluids may contain one or more viscosifiers or suspending agents in addition to the polysaccharide required, weighting agents, corrosion
  • inhibitors soluble salts, biocides, fungicides, seepage loss control additives, bridging agents, deflocculants, lubricity additives, shale control additives, pH
  • control additives and other additives as desired.
  • the borehole fluids may contain one or more materials which function as
  • humic acid salts lignite salts
  • hgnosulfonates gums, synthetic water
  • the fluids of this invention preferably have a pH in the range from about 7.5 to about 11.5, most preferably from 8 to about 11.
  • the pH can be obtained as is well known in the art by the addition of bases to the fluid, such as potassium hydroxide, potassium carbonate, potassium humate, sodium hydroxide, sodium
  • the preferred base is magnesium hydroxide.
  • this invention significantly enhances the thermal stability of the ELSRV fluids.
  • magnesium oxide enhances the thermal stability of
  • aqueous fluids containing polysaccharide polymers such as xanthan gum, hydroxy- ethylcellulose, and the like.
  • polysaccharide polymers such as xanthan gum, hydroxy- ethylcellulose, and the like.
  • the magnesium oxide functions as an alkaline buffer to prevent the pH of the fluid from decreasing appreciably upon
  • water soluble potassium compounds can be incorporated into the
  • potassium chloride potassium formate, potassium acetate, and the like to fluids to enhance the shale stabilizing characteristics of the fluids.
  • the borehole fluids of this invention contains an aqueous phase which may be
  • the formulated brine is manufactured by
  • soluble salts dissolving one or more soluble salts in water, a natural brine, or sea water.
  • Representative soluble salts are the chloride, bromide, acetate and formate salts of potassium, sodium, calcium, magnesium and zinc.
  • the fluids may be prepared by mixing with the aqueous phase the desired components in any order, except for the weight material, if used, which is generally added last such that it will remain suspended in the fluid.
  • the OSM may be added
  • water soluble salts are added to provide a formulated brine aqueous phase, it is
  • water soluble salts be added after the other desired components
  • the borehole fluid of this invention is circulated within a borehole during well
  • the OSM and the polysaccharide viscosifier are mixed together prior to their addition to the aqueous fluid.
  • additive mixture will contain from about 0.15 part by weight of the OSM per part of the polysaccharide, to about 15 parts about by weight of the OSM per part of the
  • polysaccharide preferably from about 0.3 part by weight of the OSM per part of
  • the polysaccharide to about 10 parts by weight of the OSM per part by weight of
  • Brookfield Viscometer which is the ratio of the 0.5 rpm viscosity to the 100
  • Biopolymer II which is BIOZAN, a product of the Kelco Oil Field Group, Inc.; Bill
  • Example 1 Various fluids were prepared as in Example 1. The initial rheology and the
  • Example 1 Various fluids were prepared using the procedure set forth in Example 1.
  • the fluids contained either Biopolymer I or Biopolymer II, and various concentrations of the OSM, magnesium oxide, or zinc oxide as set forth in Table C.
  • the rheology was prepared using the procedure set forth in Example 1.
  • the fluids contained either Biopolymer I or Biopolymer II, and various concentrations of the OSM, magnesium oxide, or zinc oxide as set forth in Table C.
  • Example 1 Example 1
  • Fluids were prepared as in Example 1 containing 4.285 kg/m 3 (1.5 ppb) pf XANVIS xanthan gum (Biopolymer III) and the concentrations of MgO and OSM set forth in Table F. The initial rheology, and the rheology and fluid loss obtained
  • Fluids were prepared as in Example 1 containing the concentrations of KELZAN XCD xanthan gum, magnesium oxide, and OSM set forth in Table G.

Abstract

Disclosed is a method of increasing the thermal stability or decreasing the fluid loss of aqueous polysaccharide-containing fluids which comprises incorporating into the fluids an oligosaccharide mixture composed of arabinose, mannose, galactose, glucose, and xylose sugar units, the oligosaccharide mixture consisting of the water soluble portion of thermally hydrolyzed lignocellulose and consisting primarily of pentosans and hexosans containing from one to four combined sugar units. Preferred fluids contain a biopolymer which increases the low shear rate viscosity of the fluids. Fluids which contain polysaccharides which impart other desirable characteristics to the fluids, such as increased viscosity at higher shear rates, fluid loss control, and the like, also exhibit increased thermal stability upon incorporating the oligosaccharide mixture therein.

Description

POLYSACCHARIDE-CONTAINING WELL DRILLING
AND SERVICING FLUIDS Field Of The Invention
The invention relates to fluids used in the drilling and/or servicing of oil and/or gas wells, and particularly drilling fluids, drill-in fluids, workover fluids,
completion fluids, perforating fluids, and the like. The invention provides
enhanced thermal stability and decreased fluid loss to such fluids which have been viscosified with a polysaccharide polymer which increases the low shear rate
viscosity of the fluids. Background Of The Invention
It is known to produce viscoelastic fluids for use in oil well drilling and
servicing, especially for the so called "drill-in" fluids used in horizontal drilling within a hydrocarbon-bearing formation. See for example the following
references: "Drill-In Fluids Improve High Angle Well Production," p. 5-11,
Supplemental to the Petroleum Engineer International, March, 1995; and "Soluble
Bridging Particle Drilling System Generates Successful Completions In
Unconsolidated Sand Reservoirs," Jay Dobson and Delton Kayga, presented at the
5th International Conference On Horizontal Well Technology, Amsterdam, The
Netherlands, July 14-16, 1993. Such fluids are characterized as having a rheological profile which is shear
thinning, having a high viscosity at extremely low shear rates and a low viscosity at
high shear rates. Thus such fluids are pseudoplastic having a high yield stress. This type of rheology is produced by hydrating in the fluid certain water soluble polymers. These polymers are biopolymers. i.e., microbially produced polysaccharides or heteropolysaccharides, and are well known in the art.
It is well known that polysaccharides are degraded by heat as the temperature of the fluid containing them is increased. The thermal degradation of the polysaccharides decreases the viscosity of the fluid, most especially the low shear
rate viscosity which provides the fluid with its desirable characteristics as many other water soluble polymers and other materials can provide the high shear rate
viscosity required. U.S. Patent No. 5,514,644 discloses the use of magnesia and a thiosulfate salt
to enhance the thermal stability of polysaccharide-containing, saturated salt brines.
It is disclosed in the article "Biopolymer Solution Viscosity Stabilization-Polymer
Degradation and Antioxidant Use," Scott L. Wellington, Society of Petroleum
Engineers Journal, December, 1983, pp. 901-912, that a combination of a free
radical transfer agent, a sacrificial easily oxidizable alcohol, a compatible oxygen scavenger, and a sufficient brine concentration were required to stabilize xanthan
gum-containing fluids. U.S. Patent No. 4.485.020 discloses the preparation of a
thermostable, viscous xanthan gum solution by heating a xanthan gum solution in
the presence of at least one Ci to Cio alkyl or C to Cι0 cycloaklyl substituted
primary or secondary mono- or diamine having an upper limit of a total of 15
carbon atoms at a temperature in the range of about 30° to about 130°C from about
5 minutes to 120 minutes. U.S. Patent No. 4.900.457 discloses that the thermal stability of aqueous polysaccharide solutions can be significantly enhanced by incorporating certain formate salts therein.
Thus there is a need for enhancing the thermal stability of polysaccharide-
containing aqueous fluids, particularly at low concentrations of soluble salts dissolved therein.
Summary of the Invention
I have found that the stability to thermal degradation of polysaccharide-
containing aqueous fluids which exhibit an enhanced low shear rate viscosity, which may hereinafter be referred to as ELSRV fluids, is enhanced, and the fluid loss is reduced, by adding to the ELSRV fluid an oligosaccharide mixture
composed of arabinose, mannose, galactose, glucose, and xylose sugar units,
consisting primarily of pentosans and hexosans containing from one to four
combined sugar units, the oligosaccharide mixture preferably consisting of the water soluble portion of thermally hydrolyzed lignocellulose. For the purpose of
this invention, the ELSRV fluids have a shear thinning index of at least 10,
wherein the shear thinning index is the ratio of the Brookfield viscosity of a fluid at
0.5 rpm to the viscosity of the fluid at 100 rpm, and is indicative of the shear
thinning characteristics of the fluid, preferably at least 20.
The oligosaccharide mixture also enhances the thermal stability of
polysaccharide-containing aqueous fluids which do not exhibit an enhanced low
shear rate viscosity such as fluids containing cellulose derivatives. It is an object of this invention to provide a process for enhancing the thermal stability of aqueous polysaccharide-containing fluids as evidenced by the low shear
rate viscosity of the fluids, and the fluids prepared thereof.
It is another object of this invention to provide a process for enhancing the
thermal stability of aqueous fluids containing polysaccharides which do not exhibit an elevated low shear rate viscosity, and the fluids prepared thereby.
It is also an object of the invention to provide a process for decreasing the fluid
loss of aqueous polysaccharide-containing fluids, and the fluids prepared thereof. While the invention is susceptible of various modifications and alternative
forms, specific embodiments thereof will hereinafter be described in detail and
shown by way of example. It should be understood, however, that it is not
intended to limit the invention to the particular forms disclosed, but, on the contrary, the invention is to cover all modifications and alternatives falling within the spirit and scope of the invention as expressed in the appended claims.
The compositions can comprise, consist essentially of, or consist of the stated
materials. The method can comprise, consist essentially of, or consist of the stated
steps with the stated materials.
Preferred Embodiments of the Invention
The oligosaccharide mixture (hereinafter sometimes referred to as "OSM")
useful in the present invention is preferably obtained from the thermal hydrolysis of
lignocellulose materials. The thermal hydrolysis may be carried out in any one of
several manners such as by subjecting wood of trees and woody materials of corn stalks, cane, and other vegetable growths to the action of steam under elevated
temperatures and pressures. The OSM may also be obtained by acid hydrolysis of lignocelluloses as well as by saccharification of wood. Preferably, however, the thermal hydrolysis is carried out by charging wood chips to a closed chamber (e.g.,
a gun as set forth in Mason U.S. Patent No. 1,824,221, incorporated herein by reference), subjecting the chips to pressure of about 200-1200 pounds per square
inch and a temperature of about 200-300°C for approximately 30 minutes to 5
seconds, respectively, in the presence of steam, and then discharging the woody
material from the gun through a constricted discharge means therein into a zone of lower pressure, preferably atmospheric pressure, thereby exploding the wood chips
into comparatively finely divided elongated fibers. Under this treatment the wood undergoes hydrolysis, and water-insoluble and readily hydrolyzable constituents
thereof are rendered soluble or dispersible in water. These water solubles are
removed from the fiber, which may be accomplished by washing the fiber in water or by squeezing the fiber with rolls and/or screws and the like apparatus. See for
example Boehm U.S. Patent No. 2,224,135, incorporated herein by reference. The
water solubles can be concentrated or rendered solid by removing w ater therefrom,
as by evaporation, drying, etc.
Water solubles resulting from such hydrolysis of lignocellulose materials as a class are applicable to this invention. A typical analysis of the water solubles, the
OSM of this invention, made from pine wood is as follows: hexosans and
pentosans. 70% by weight; lignin, 15% by weight: non-sugar carbohydrates, 10% by weight; and gums, 5% by weight. The constituents of the OSM will vary somewhat depending on the type of lignocellulose material hydrolyzed and the
conditions, e.g., time, temperature, pressure, etc. Depending upon these conditions, the constituents of the OSM can vary roughly as follows: pentosans and hexosans, 60-80%) by weight; lignin, 5-25% by weight; non-sugar
carbohydrates, 5-15% by weight; and gums, 2-8% by weight. The pentosans and
hexosans contain primarily from one to about four combined sugar units composed of arabinose, mannose, galactose, glucose, and xylose sugar units.
It has been disclosed in Fuller U.S. Patent No. 2,713,029 and Brink et al. U.S.
Patent No. 2,713,030 that the addition of small amounts of the OSM to clay-water drilling mud systems, such as from about 0.07-1.75 pounds of OSM per 42 gallon
barrel of mud, imparts thereto low viscosity and gel strength.
Incorporation of the OSM into aqueous ELSRV well drilling and servicing
fluids which contain one or more polysaccharides hydrated (solublized or
dispersed) therein enhances the thermal stability of the fluids as measured by the
low shear rate viscosity, i.e., the viscosity at less than about one sec" 1.
The minimum concentration of the OSM incorporated into the aqueous polysaccharide-containing fluids is that amount, as determined by routine testing,
which increases the thermal stability of the fluid and/or which decreases the fluid
loss of the fluid. In the case of ELSRV fluids, this is determined by evaluating the low shear rate viscosity of the fluid and the fluid loss after aging at the desired
temperature and comparing the results obtained with those of the fluid which does not contain the OSM. In the case of fluids containing polysaccharides which do not significantly enhance the low shear rate viscosity of the fluids, the thermal stability can be determined by evaluating other properties of the fluids such as the viscosity at higher shear rates, fluid loss, and the like, and comparing the results
obtained with those of the fluid which does not contain the OSM.
Generally the concentration of the OSM will be from about 0.7 kg/m3 (0.25
ppb) to about 428 kg/m3 (150 ppb), preferably from about 1.4 kg/m3 (0.5 ppb) to
about 171 kg/m (60 ppb), most preferably from about 1.4 kg/m (0.5 ppb) to about
57 kg/m3 (20 ppb).
The polymers useful in the ELSRV fluids of this invention comprise any water soluble polymer which increases the low shear rate viscosity of the fluid to produce
a fluid exhibiting a high yield stress, shear thinning behavior. Particularly useful
are biopolymers produced by the action of bacteria, fungi, or other microorganisms on a suitable substrate. Exemplary biopolymers are the polysaccharides produced
by the action of Xanthomonas compestris bacteria which are known as xanthan
gums. These are available commercially from several sources including: Kelco Oil Field Group, Inc., under the trademarks "Xanvis" and "Kelzan"; Rhone-Poulenc
Chimie Fine, under the trademark "Rhodopol 23-p"; Pfizer Inc., under the
trademark "Flocon 4800C"; Shell International Chemical Company of London,
U.K., under the trademark "Shellflo ZA"; and Drilling Specialties Company, under
the trademark "Flowzan." See for example U.S. Patent No. 4,299.825 and U.S.
Patent No. 4,758,356, each incorporated herein by reference. Other biopolymers useful in the fluids of this invention are the so-called welan gums produced by fermentation with a microorganism of the genus Alcaligenes. See for example
U.S. Patent No. 4,342,866, incorporated herein by reference. Gellan gums are disclosed in U.S. Patent No. 4,503,084, incorporated herein by reference.
Scleroglucan polysaccharides produced by fungi of the genus sclerotium are
disclosed in U.S. Patent No. 3,301,848, incorporated herein by reference. Commercially available scleroglucan is sold under the trademarks "Polytran" from the Pillsbury Company and "Actigum CS-11" from CECA S.A. Succinoglycan
polysaccharides are produced by cultivating a slime-forming species of Pesudomonas, Rhizobium, Alcaligenes or Agrobacterium, e.g., Pseudoraonas sp.
NCIB 11264, Pseudomonas sp. NCIB 11592 or Agrobacterium radiobacter NCIB
11883, or mutants thereof, as described in European Patent No. A40445 or A138255. Commercially available succinoglycan biopolymer is sold by Shell
International Chemical Company of London, U.K., under the trademark "Shellflo-
S".
Other polysaccharides added to aqueous base borehole fluids IO provide characteristics to the fluids other than increasing the low shear rate viscosity
include: cellulose derivatives, such as carboxymethyl cellulose, hydroxyethyl
cellulose, mixed ethers, and the like; starch derivatives such as carboxymethyl
starch, hydroxyethyl starch, hydroxypropyl starch, mixed ethers, and the like,
including the partially crosslinked derivatives thereof; guar gum and derivatives
thereof; and other polysaccharides as are well known in the art. Such polysaccharides may increase the viscosity at higher shear rates, decrease the fluid loss, or provide other characteristics to the fluids.
The minimum concentration of the polymer required to increase the low shear rate viscosity of the fluid can be determined by routine testing. Thus the minimum
concentration will be an amount sufficient to impart to the fluid the desired low shear rate viscosity. Generally the fluids will contain a concentration from about
0.7 kg/m3 (0.25 ppb) to about 17.1 kg/m3 (6 ppb), preferably from about 1.4 kg/m3
(0.5 ppb) to about 14.25 kg/m3 (5 ppb).
The water base borehole fluids of this invention generally will contain
materials well known in the art to provide various characteristics or properties to the fluid. Thus the fluids may contain one or more viscosifiers or suspending agents in addition to the polysaccharide required, weighting agents, corrosion
inhibitors, soluble salts, biocides, fungicides, seepage loss control additives, bridging agents, deflocculants, lubricity additives, shale control additives, pH
control additives, and other additives as desired.
The borehole fluids may contain one or more materials which function as
encapsulating or fluid loss control additives to restrict the entry of liquid from the
fluid to the contacted shale. Representative materials known in the art include
partially solublized starch, gelatinized starch, starch derivatives, cellulose
derivatives, humic acid salts (lignite salts), hgnosulfonates, gums, synthetic water
soluble polymers, and mixtures thereof. The fluids of this invention preferably have a pH in the range from about 7.5 to about 11.5, most preferably from 8 to about 11. The pH can be obtained as is well known in the art by the addition of bases to the fluid, such as potassium hydroxide, potassium carbonate, potassium humate, sodium hydroxide, sodium
carbonate, sodium humate, magnesium oxide, calcium hydroxide, zinc oxide, and
mixtures thereof. The preferred base is magnesium hydroxide.
It has been determined that magnesium oxide in combination with the OSM of
this invention significantly enhances the thermal stability of the ELSRV fluids.
It has long been known that magnesium oxide enhances the thermal stability of
aqueous fluids containing polysaccharide polymers such as xanthan gum, hydroxy- ethylcellulose, and the like. Presumably the magnesium oxide functions as an alkaline buffer to prevent the pH of the fluid from decreasing appreciably upon
aging the fluid at elevated temperatures.
If desired, water soluble potassium compounds can be incorporated into the
fluids of this invention to increase the potassium ion content thereoi". Thus it is
known to add potassium chloride, potassium formate, potassium acetate, and the like to fluids to enhance the shale stabilizing characteristics of the fluids.
The borehole fluids of this invention contains an aqueous phase which may be
fresh water, a natural brine, sea water or a formulated brine in which the
polysaccharide and OSM are solublized. The formulated brine is manufactured by
dissolving one or more soluble salts in water, a natural brine, or sea water. Representative soluble salts are the chloride, bromide, acetate and formate salts of potassium, sodium, calcium, magnesium and zinc.
The fluids may be prepared by mixing with the aqueous phase the desired components in any order, except for the weight material, if used, which is generally added last such that it will remain suspended in the fluid. The OSM may be added
to the aqueous phase before or after any of the desired components are added. If
water soluble salts are added to provide a formulated brine aqueous phase, it is
preferred that the water soluble salts be added after the other desired components,
except the weight material, have been mixed. The borehole fluid of this invention is circulated within a borehole during well
drilling or servicing operations as is well known in the art.
In a preferred embodiment of the invention, the OSM and the polysaccharide viscosifier are mixed together prior to their addition to the aqueous fluid. Thus this
additive mixture will contain from about 0.15 part by weight of the OSM per part of the polysaccharide, to about 15 parts about by weight of the OSM per part of the
polysaccharide, preferably from about 0.3 part by weight of the OSM per part of
the polysaccharide to about 10 parts by weight of the OSM per part by weight of
the polysaccharide.
In order to more completely describe the invention, the following non-limiting examples are given. In these examples and in this specification, the following
abbreviations may be used: cc = cubic centimeters; g = gram; kg = kilogram; m3 =
cubic meter; ppb = pounds per 42 gallon barrel; PV = API plastic viscosity in centipoise; YP = API yield point in pounds per 100 square feet; rpm = revolutions per minute; LSRV = low shear rate viscosity in centipoise as determined with a Brookfield RV-1 Viscometer at 0.5 rpm; STI = the shear thinning index obtained
with a Brookfield Viscometer, which is the ratio of the 0.5 rpm viscosity to the 100
rpm viscosity; BI = Biopolymer I which is KELZAN XCD xanthan gum; BII =
Biopolymer II which is BIOZAN, a product of the Kelco Oil Field Group, Inc.; Bill
= Biopolymer III which is XANVIS, a xanthan gum; STS = sodium thiosulfate; OSM = oligosaccharide mixture as set forth hereinbefore.
The plastic viscosity, yield point. 3 rpm viscosity, and fluid loss were
determined by the procedures set forth in the American Petroleum Institute's Recommended Practice 13B-1.
Example 1
Various aqueous fluids were prepared by adding to 350 milliliters of water
mixing at low shear in a Waring Blendor (sufficient to form a vortex) the
concentrations of Biopolymer I, OSM, and magnesium oxide set forth in Table A.
The fluids were then mixed five minutes at moderate shear, placed in glass jars,
capped, and aged for 16 hours at 82.2°C (180°F). The API rheology and low shear
rate rheology were obtained after the fluids were cooled to room temperature and
mixed well by hand shaking. The data obtained are set forth in Table A. Example 2
Various fluids were prepared as in Example 1. The initial rheology and the
rheology obtained after aging for 16 hours at 82.2°C is set forth in Table B. Example 3
Various fluids were prepared using the procedure set forth in Example 1. The fluids contained either Biopolymer I or Biopolymer II, and various concentrations of the OSM, magnesium oxide, or zinc oxide as set forth in Table C. The rheology
data obtained initially and after aging for 16 hours at 82.2°C are set forth in Table
C.
Example 4
Various fluids containing 4.285 kg/m3 (1.5 ppb) Biopolymer I and 2.857 kg/m3 (1.0
ppb) magnesium oxide were prepared as in Example 1. The fluids additionally
contained the concentrations of the OSM and sodium thiosulfate set forth in Table D. The low shear rate viscosity and thixotropic index of the fluids before and after
aging at 82.2°C for 16 hours are set forth in Table D.
Example 5
Fluids containing 4.285 kg/m (1.5 ppb) of various polysaccharides which do
not appreciably increase the low shear rate viscosity but which provide other desired properties such as enhanced viscosity at higher shear rates, fluid loss
control, and the like, were prepared as in Example 1. The fluids additionally
contained the concentrations of sodium hydroxide, magnesium oxide, and the OSM
set forth in Table E. The rheological data obtained after aging the fluids at 82.2°C
for 16 hours are set forth in Table E. Example 6
Fluids were prepared as in Example 1 containing 4.285 kg/m3 (1.5 ppb) pf XANVIS xanthan gum (Biopolymer III) and the concentrations of MgO and OSM set forth in Table F. The initial rheology, and the rheology and fluid loss obtained
after aging the fluids for 16 hours at 82.2°C is set forth in Table F. The data
obtained are set forth in Table F.
Example 7
Fluids were prepared as in Example 1 containing the concentrations of KELZAN XCD xanthan gum, magnesium oxide, and OSM set forth in Table G.
The fluids were evaluated as in Example 6. The data obtained are set forth in
Table 6.
Table A
Composition
Water, cc 350 350 350 350 350 350 350 350 350
BL g 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 OSM, g 0 10 20 0 0.2 0.5 10 20 60
MgO, g 0 0 0 2 2 2
Rheology After Aging 16 Hours at 82.2°C (180°F)
PV 12 11 4.5 10 6.5 8 33
YP 23 23 12.5 12 18 18.5 23 41 3 rpm 1 10 8.5 3 4.5 7.5 8.5 10 18.5
LSRV (xl0"3) 0.2 17 14 0.8 2.6 9.2 10.4 15 40
STI 3.9 54.8 50.3 6.5 20 41.8 44.8 53.5 63
Table B
Composition
Water, cc 350 350 350 350 350 350 350
BL g 2.5 2.5 2.5
OSM, g 10 10 10
MgO, g
Initial Rheology
PV 6.5 7.5 7
YP 22 22 53 30 30 61 3 rpm 13 12 16 20 17.5 20.5
LSRV (xlO"3) 33.2 25.6 46.2 52.4 42.8 78
STI 108.9 85.3 89.7 117.8 97.7 1 1 1.4
Rheology After Aging 16 Hours at 82.2°C (180°F)
PV 5 4.5 10 5.5 4.5 1 1.5 8.5
YP 13 15.5 30 19 21.5 34.5 12.5
3 rpm 16 7 13.5 20.5 5.5
LSRV (xl0"3) 0.64 5.6 40.6 2.64 18.0 53.6 10.0
STI 4.8 26.9 91.9 11.8 55.6 100.8 61.0
Table C
Composition 1 2 3 4 5 6 7 8 9
Water, cc 350 350 350 350 350 350 350 350 350
BI, g 1.5 1.5 1.5 1.5 1.5 1.5 1.5 0 0
BII, g 0 0 0 0 0 0 0 1.5 1.5
OSM, g 0 0.5 10 0 0 0.5 10 0 0.5
MgO, g 0 0 0 0 1.0 1.0 1.0 1.0 1.0
ZnO, g 2.0 2.0 2.0 0 0 0 0 0 0
Initial Rheology
PV 5.5 8.5 9.5 5 5 7 8 5.5 6.5
YP 14.5 17.5 17 15.5 16 15 16 12 14.5
3 rpm 8 10 8.5 9 8 7 7.5 5 6
LSRV (xlO"3) 17.6 21.1 20.8 19.2 13.6 14.4 17.4 6.4 8.6
STI 88.0 82.1 86.0 93.7 65.7 70.9 81.3 45.7 48.9
Rheology After Ag ing 16 Hours at 82.2°C (180°F
PV 4.5 4.5 6.5 6.5
YP 11 18 1 1 11.5 16 11 13 3 rpm 8.5 1.5 4.5 5.5
LSRV (xl0 ,"-J3)N 0.9 1.9 16.6 0.28 4.6 15.2 5.2 7.8 STI 9.0 14.7 74.1 3.4 10. 32.9 74.5 39.4 48.7 Table D
Composition
Water, cc 350 350 350 350 350 350
BI, g 1.5 1.5 1.5 1.5 1.5 1.5
MgO, g 1.0 1.0 1.0 1.0 1.0 1.0
STS, g 3.0 3.0 0
OSM, g 10.0 0.5 2.5 10.0
Initial Rheology
LSRV(xlO"3) 13.6 14.2 18.0 20.6 19.8 17.7
STI 65.7 75.5 84.9 89.2 86.8 82.7
Rheology After Aging 16 Hours at 82.2°C (180°F)
LSRV (xl0"3) 1.2 6.8 17.1 11.6 12.4 18.4
STI 10.3 42.2 80.7 54.5 61.4 83.6
Table E
Composition 1 4 7 8
Water, cc 350 350 350 350 350 350 350 350
Polyanionic Cellulose, g 1.5 1.5 1.5 0 0 0 0 0
Modified Polysaccharide Gum, g 0 0 0 0 0 1.5 1.5 1.5 0 0
Hydroxethyl Cellulose, g 0 0 0 0 0 0 1.5 1.5
NaOH, g 1 1 0 1 1 0 0 0
MgO, g 0 0 2 0 0 2 1 1
OSM, g 0 10 10 0 10 10 0 5
Rheology After Aging 16 Hours at 82.2°C (180°F)
PV 5 14.5 15 7 10.5 14.5 13 17.5
YP 0 13.5 12 1 15 24.5 22 32.5
3 rpm 0.5 1 0.5 1 3.5 LSRV 40 100 200 50 190 40 300 700
STI 1.5 1.2 2.1 1.5 1.7 2.1 2.1 2.8
Table F
Composition 1 2 3 4
Water, cc 350 350 350 350
Bill, g 1.5 1.5 1.5 1.5
MgO, g 0 1.0 1.0 1.0
OSM, g 0 0 0.5 10.0
Initial Rheology
LSRV (xlO"3) 11.9 8.4 14.9 28.9
STI 88.9 66.7 59.2 79.3
PV 5 4 7 11
YP 12 14 17 27
3 rpm 10 8 8.5 15
Properties After Hot Rolling 16 Hours at l80°F
LSRV (xlO'3) 0.3 0.9 2.5 24.0
STI 3.8 8.8 17.7 46.6
PV 4 4 5 14
YP 11 11 13 24
3 rpm 5 5 16
Fluid Loss, cc 48 84 20 9
Table G
Composition 2 4 5 6
KELZAN XCD, g 1.0 1.0 1.5 1.5 2.0 2.0
MgO, g 0.67 0.67 1.00 1.00 1.33 1.33
OSM, g 0.33 10.33 0.50 10.50 0.67 10.67
Initial Rheology
PV, cp 8 14 8 14
YP, lb/100 ft2 10 10 13 12 20 22
3 rpm 5 6 10 10 14 17 LSRV (xlO"3), cp 2.2 3.6 7.5 13.2 23.2 28.8
STI 18.3 26.5 40.0 54.1 76.6 62.6
Rheology After Aging 16 Hours at 82.2°C (180°F
PV, cp 3 5 4 8 5 15
YP, lb/100 ft2 9 10 12 17 19 15
3 rpm 3 6 6 10 11 16
LSRV (xlO"3), cp 0.8 3.2 11.7 9.5 24.8
STI 8.3 . 20.7 24.5 45.8 37.9 69.5
API Fluid Loss, cc 22 12 21 9.4 18 9.7

Claims

What is claimed is:
1. In an aqueous-base drilling fluid for the drilling or servicing of oil or gas
wells comprising an aqueous liquid having incorporated therein one or more
polysaccharides in an amount to increase the low shear rate viscosity of the aqueous-base fluid, the improvement which comprises incorporating into the
aqueous-base fluid an oligosaccharide mixture composed of arabinose, mannose,
galactose, glucose, and xylose sugar units, the oligosaccharide mixture consisting of pentosans and hexosans containing from one to four combined sugar units,
wherein the concentration of the oligosaccharide mixture is sufficient to increase the thermal stability or decrease the fluid loss of the fluid.
2. The fluid of Claim 1 wherein there is added at least about 0.7 kg/mJ of the
oligosaccharide mixture.
3. The fluid of Claim 1 wherein there is added from about 1.4 kg/ m3 to about
428 kg/mJ of the oligosaccharide mixture.
4. The fluid of Claim 1 wherein there is added from about 1.4 kg/ m3 to about
57 kg/mJ of the oligosaccharide mixture.
5. The fluid of Claim 1 which has a pH from about 7.5 to about 11.5.
6. The fluid of Claim 1 which has a pH from about 8 to about 1 1.
7. The fluid of Claim 5 which contains magnesium oxide.
8. The fluid of Claim 6 which contains magnesium oxide.
9. The fluid of Claim 1 wherein the polysaccharide is a biopolymer which
imparts an elevated low shear rate viscosity to the fluid as evidenced by the fluid
having a shear thinning index greater than about 10.
10. The fluid of Claim 9 wherein the biopolymer is xanthan gum.
11. In an aqueous base fluid for the drilling or servicing of oil or gas wells
comprising an aqueous liquid having incorporated therein one or more
polysaccharides in an amount to increase the low shear rate viscosity, increase the
high shear rate viscosity, or decrease the fluid loss of the fluid, the improvement which comprises incorporating into the aqueous-base fluid an oligosaccharide mixture composed of arabinose. mannose, galactose, glucose, and xylose sugar
units, the oligosaccharide mixture consisting of pentosans and hexosans containing from one to four combined sugar units, wherein the concentration of the oligosaccharide mixture is sufficient to increase the thermal stabilit╬╗ of the fluid.
12. The fluid of Claim 11 wherein there is added at least about 0.7 kg/m3 of
the oligosaccharide mixture.
13. The fluid of Claim 11 wherein there is added from about 1.4 kg/ m3 to
about 57 kg/m3 of the oligosaccharide mixture.
14. The fluid of Claim 11 wherein the polysaccharide is a biopolymer which
imparts an elevated low shear rate viscosity to the fluid as evidenced by the fluid
having a shear thinning index greater than about 10.
15. The fluid of Claim 14 wherein the biopolymer is a xanthan gum.
16. The fluid of Claim 11 wherein the polysaccharide is a cellulose derivative.
17. The method of enhancing the thermal stability or decreasing the fluid loss of an aqueous fluid having incorporated therein one or more polysaccharides in an
amount sufficient to provide the fluid with the characteristics desired, the improvement which comprises incorporating into the aqueous-base fluid an oligosaccharide mixture composed of arabinose, mannose, galactose, glucose, and xylose sugar units, the oligosaccharide mixture consisting of pentosans and
hexosans containing from one to four combined sugar units, wherein the
concentration of the oligosaccharide mixture is sufficient to increase the thermal
stability or decrease the fluid loss of the fluid.
18. The method of Claim 17 wherein there is added at least about 0.7 kg/m3 of the oligosaccharide mixture.
19. The method of Claim 17 wherein there is added from about 1.4 kg/ m3 to about 428 kg/m3 of the oligosaccharide mixture.
20. The method of Claim 17 wherein there is added from about 1.4 kg/ m3 to about 57 kg/m3 of the oligosaccharide mixture.
21. The method of Claim 17 wherein the polysaccharide is a biopolymer produced by the action of bacteria, fungi, or other microorganisms on a suitable
substrate.
22. The method of Claim 21 wherein the biopolymer is xanthan gum.
PCT/US1999/010047 1998-07-24 1999-05-07 Polysaccharide-containing well drilling and servicing fluids WO2000005322A1 (en)

Priority Applications (9)

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EA200100181A EA002815B1 (en) 1998-07-24 1999-05-07 Polysaccharide-containing oil and gas well drilling and servicing fluids, method of increasing the thermal stability or decreasing the fluid loss of aqueous-base fluids
CA002338444A CA2338444C (en) 1998-07-24 1999-05-07 Polysaccharide-containing well drilling and servicing fluids
AU38903/99A AU3890399A (en) 1998-07-24 1999-05-07 Polysaccharide-containing well drilling and servicing fluids
DE69922670T DE69922670D1 (en) 1998-07-24 1999-05-07 POLYSACCHARIDE CONTAINING DRILLING AND MAINTENANCE LIQUIDS
EP99921783A EP1114115B1 (en) 1998-07-24 1999-05-07 Polysaccharide-containing well drilling and servicing fluids
MXPA01000839A MXPA01000839A (en) 1998-07-24 1999-05-07 Polysaccharide-containing well drilling and servicing fluids.
AT99921783T ATE284936T1 (en) 1998-07-24 1999-05-07 DRILLING AND SERVICE FLUIDS CONTAINING POLYSACCHARIDE
BRPI9912417-3A BR9912417B1 (en) 1998-07-24 1999-05-07 aqueous based fluid for drilling or maintaining oil or gas wells, and process for improving thermal stability or decreasing fluid loss of an aqueous liquid.
NO20010384A NO330308B1 (en) 1998-07-24 2001-01-23 Polysaccharide-containing wellbore and service fluids

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