WO2004061046A1 - Aerogels effective to reduce drilling fluid density - Google Patents

Aerogels effective to reduce drilling fluid density Download PDF

Info

Publication number
WO2004061046A1
WO2004061046A1 PCT/US2003/041734 US0341734W WO2004061046A1 WO 2004061046 A1 WO2004061046 A1 WO 2004061046A1 US 0341734 W US0341734 W US 0341734W WO 2004061046 A1 WO2004061046 A1 WO 2004061046A1
Authority
WO
WIPO (PCT)
Prior art keywords
system fluid
aerogels
fluids
fluid
density
Prior art date
Application number
PCT/US2003/041734
Other languages
French (fr)
Other versions
WO2004061046B1 (en
Inventor
Charles W. Alsobrook
Thomas A. Jones
Original Assignee
Baker Hughes Incorporated
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 Baker Hughes Incorporated filed Critical Baker Hughes Incorporated
Priority to AU2003300150A priority Critical patent/AU2003300150A1/en
Publication of WO2004061046A1 publication Critical patent/WO2004061046A1/en
Publication of WO2004061046B1 publication Critical patent/WO2004061046B1/en

Links

Classifications

    • 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
    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/502Oil-based compositions
    • 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
    • C09K8/03Specific additives for general use in well-drilling compositions
    • C09K8/032Inorganic additives
    • 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
    • C09K8/03Specific additives for general use in well-drilling compositions
    • C09K8/035Organic additives
    • 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
    • C09K8/32Non-aqueous well-drilling compositions, e.g. oil-based
    • C09K8/34Organic liquids
    • 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
    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504Compositions based on water or polar solvents
    • 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
    • C09K8/52Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • 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
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/18Bridging agents, i.e. particles for temporarily filling the pores of a formation; Graded salts

Abstract

Use of aerogels reduce the density of system fluids useful during drilling operations and system fluids comprising aerogels.

Description

TITLE: AEROGELS EFFECTIVE TO REDUCE DRILLING FLUID
DENSITY
Field of the Application
The present application relates to the use of aerogels to reduce the density of system fluids useful during drilling operations. Background of the Application
Low density fluid systems reduce the volume of fluid invasion into a producing reservoir, thus minimizing damage to the pay zone. More importantly, fluid systems with very low densities can be used to drill reservoirs in underbalanced pressure conditions that virtually eliminate invasion and damage to the reservoir. Low density system fluids having effective rheology which may be produced at relatively low cost are always needed. Summary of the Application
The present application provides a method for reducing density of a system fluid useful during drilling operations. The method comprises providing a quantity of a system fluid comprising an amount of one or more aerogels, the system fluid having effective rheology and lubricity properties and having a reduced density compared to the same system fluid absent the one or more aerogels.
The present application also provides a system fluid having effective rheology comprising an amount of one or more aerogels effective to reduce density of said system fluid compared to the same system fluid absent the one or more aerogels.
The system fluid is selected from the group consisting of drilling fluids, drill-in fluids, completion fluids, workover fluids, spotting fluids, and cementing fluids; preferably drilling fluids, drill-in fluids, completion fluids, workover fluids, and spotting fluids.
In one aspect, the system fluid comprises an inorganic aerogel. In another aspect, the system fluid comprises an organic aerogel.
In one aspect, the aerogel is hydrophilic. In another aspect the aerogel is hydrophobic.
In one aspect, the aerogel comprises an element selected from the group consisting of silicon, aluminum, titanium, zirconium, tin, lithium, cerium, vanadium, and mixtures thereof. In a preferred aspect, the aerogel comprises silicon, preferably silicon oxide.
In one aspect, the aerogel comprises particle sizes of up to about 200 μm. In another aspect, the aerogel comprises particle sizes of about 1 μm or more. In yet another aspect, the aerogel comprises particle sizes of from about 1 μm to about 44 μm. In another aspect, the aerogel comprises a particle size distribution effective for bridging producing formations. In yet another aspect, the aerogel comprises a particle size distribution effective for filter cake development.
In one aspect, the aerogel particles comprise a density of about 0.2 g/cm3 or less, preferably about 0.35 g/cm3 or less, more preferably from about 0.1 to about 0.35 g/cm3. In one aspect, the aerogel comprises about 90% gas or more. In another aspect, the aerogel comprises about 95% gas or more.
In another aspect, the aerogel comprises a total surface area of about 200 m /g or more. In yet another aspect, the aerogel comprises a total surface area of about 600 m2/g or more; preferably about 700 m2/g or more. In one aspect, the aerogel comprises a bubble matrix comprising retained gas selected from the group consisting of air, oxygen, helium, nitrogen, carbon dioxide, and inert or low activity gases. In another aspect, the aerogel comprises a bubble matrix comprising retained air. In yet another aspect, the aerogel comprises a bubble matrix comprising retained helium.
In one aspect, the aerogels are stable at temperatures of about 150 °C or more; at temperatures of about 250 °C or more; at temperatures of about 350 °C or more; at temperatures of about 450 °C. or more; and, in a preferred aspect, at temperatures of about 600 °C or more. A preferred aerogel is NANOGEL®. In one aspect, the amount of said aerogel is sufficient to produce a system fluid having a density of from about 1 lb/gal to about 8 lb/gal., preferably having a density of from about 3 lb/gal to about 6 lb/gal.
In one aspect, the system fluid is hydrophilic and said aerogel is hydrophilic. In another aspect, the system fluid is hydrophobic and said aerogel is hydrophobic.
In one aspect, the system fluid produces a filter cake comprising said aerogel that is converted to a gel upon exposure to one or more component selected from the group consisting of heat, a pH of from about 8 to about 13, and contact with water. In yet another aspect, a borehole comprising the filter cake comprising said aerogel is cleaned without using acid.
In one aspect, the system fluid is selected from the group consisting of water-based or oil-based fluid. In another aspect, system fluid comprises an oil selected from the group consisting of olefins, paraffins, water insoluble polyglycols, water insoluble esters, diesel, water insoluble Fischer-Tropsch reaction products, other organic materials that are non-toxic at the concentrations used, and combinations thereof.
In one aspect, the system fluid comprises one or more non-toxic synthetic olefins. In another aspect, the one or more olefins are selected from the group consisting of polyalphaolefins, linear alpha olefins, and internal olefms. In a most preferred aspect, the system fluid is selected from the group consisting of
PERFFLOW® and SCIFLOW™.
In another aspect, the amount of aerogel is sufficient to produce a system fluid having a density of from about 1 lb/gal to about 8 lb/gal, preferably from about 3 lb/gal to about 6 lb/gal. In another aspect, the amount of aerogel is from about 55 to about 62% of said system fluid. Detailed Description of the Application
The present application relates to system fluids "useful during drilling operations," including but not necessarily limited to "drilling" fluids, "drill-in" fluids, "completion" fluids, "workover" fluids, "spotting" fluids, and
"cementing'-' fluids. Preferred system fluids are drilling system fluids selected from the group consisting of "drilling" fluids, "drill-in" fluids, "completion" fluids, "workover" fluids, and "spotting" fluids.
A "drill-in" fluid is pumped through the drill pipe while drilling through the "payzone," or the zone believed to hold recoverable oil or gas. A "drilling fluid" is used to drill a borehole through the earth to reach the payzone. Typically a drilling mud is circulated down through the drill pipe, out the drill bit, and back up to the surface through the annulus between the drill pipe and the borehole wall. The drilling fluid has a number of purposes, including cooling and lubricating the bit, carrying the cuttings from the hole to the surface, and exerting a hydrostatic pressure against the borehole wall to prevent the flow of fluids from the surrounding formation into the borehole. A "completion fluid" is used to protect the "payzone" during the completion phase 5 of the well. Specially formulated fluids are used in connection with completion and workover operations to minimize damage to the formation. Workover fluids are used during remedial work in the well, such as removing tubing, replacing a pump, logging, reperforating, and cleaning out sand or other deposits. Spotting fluids are pumped downhole intermittently for various purposes. Cementing o fluids are used cement the well liner in place.
Formation damage can result when solids and/or filtrate derived from one of these system fluids invades the formation during drilling operations. Such formation damage may be minimized by treating the well in a near- balanced condition (wellbore pressure close to formation pressure). In low- 5 pressure reservoirs, the well often must be treated in an over-balanced and/or an under-balanced condition. If the well is over-balanced, the treating fluid is designed to temporarily seal perforations to prevent entry of fluids and solids into the formation. If the well is under-balanced, the treating fluid is designed to have a mud weight that generates lower hydrostatic pressure than the o reservoir pressure, to prevent entry of drilling fluid to the formation.
Low density fluid systems minimize damage to the pay zone by reducing the volume of fluid invasion into a producing reservoir. More importantly, fluid systems with very low densities can be used to drill reservoirs in underbalanced pressure conditions that virtually eliminate invasion and damage to the reservoir. The present application provides novel reduced density system fluids comprising aerogels.
The density of a system fluid relates to the amount and average specific gravity of the solids in the system. The desired density of a given system fluid 5 generally is dictated by the pressure in the formation. The present application involves the use of aerogel to reduce the density of system fluids for use during drilling operations while providing effective rheology and lubrication. Aerogels reduce the density of the system because the aerogels have a lower density than the system fluid. The aerogel may be an integral part of the system fluid, or the l o density of the system fluid may be reduced during drilling operations, for example by adding fluid comprising more of the aerogel or even adding mud- compatible aerogel to the mud pit during drilling operations.
An aerogel generally is defined as a gel with a gas, preferably air, as a dispersing agent. Aerogels generally are produced by drying a suitable gel. The
15 term "gel" refers to a coherent, rigid, continuous three-dimensional network of colloidal particles. Gels are produced by the aggregation of colloidal particles (typically under acidic conditions when neutralizing salts are absent) to form a three dimensional gel microstructure. When a gel is dried (liquid removed from the pores) by means in which the coherent gel microstructure is preserved, such
20 as by supercritical drying, a low density "aerogel" is formed.
Aerogels basically are selected from the group consisting of inorganic and organic aerogels. Organic aerogels are derived from widely diverse starting materials, e.g. melamine formaldehyde. . W. Pekala, J. Mater, Sci. 1989, 24, 3221, incorporated herein by reference. Preferred aerogels are inorganic aerogels.
Exemplary inorganic aerogels are described in S. S. Kistler, Nature 1931 , 127,741 , incorporated herein by reference. These first aerogels were produced from water glass and an acid as the starting materials. In that case, the water was exchanged for an organic solvent in the wet gels obtained and this lyogel was then super-critically dried. In this way, hydrophilic aerogels were obtained, as disclosed for example in U.S. Pat. No. 2,093,454, incorporated herein by reference. The colloidal component of inorganic aerogels generally comprises an element selected from the group consisting of silicon, aluminum, titanium, zirconium, tin, lithium, cerium, vanadium, and mixtures thereof. Methods for producing inorganic aerogels are described in H. D. Gesser, P. C. Goswarni, Chem Rev. 1989, 89, 765 et seq., incorporated herein by reference. Preferred aerogels comprise silicon, most preferably silicon oxide. Silica aerogels have highly desirable properties such as, for example, optical transparency, extremely low density, and very low thermal conductivity. The size of the aerogel particles is not critical, and can range from about less than 1 μm to about 200 μm, preferably from about 1 μm to about 44 μm. Preferably, the aerogels have a particle size distribution effective to promote bridging and filter cake development, where needed. If the system is underbalanced, a filter cake is not required. However, where a system is near balanced or overbalanced, the filter cake will be required, and the particle size of the aerogel preferably is from about 1 to about 200 μm. The silica aerogel particles can have any density less than the density of the particular system fluid. For most system fluids, suitable densities for the aerogel are about 0.2 g/cm3 or less, 0.35 g/cm3 or less, more preferably from about 0.1 to about 0.35 g/cm3. The aerogels comprise at least about 90% gas, preferably from about 95.0%o to about 99.0% gas, retained in the bubble matrix. The bubble matrix results in a substantial total surface area, typically about 200 m2/g or more. Preferably, the internal surface area is about 600 m2/g or more, more preferably about 700 m2/g. or more. The surface area is calculated based on the amount of nitrogen adsorbed at five different relative pressures over the range 0.05 to 0.25 according to the Brunauer-Emmett-Teller (BET) model, which is referenced in Gregg, S. J. and Sing, K. S. W, "Adsorption, Surface Area and Porosity," p. 285, Academic Press, New York (1991), incorporated herein by reference.
The gas contained in the bubble matrix of the aerogel generally is air; however, the gas may be substantially any environmentally compatible gas, including but not necessarily limited to air, oxygen, helium, nitrogen, carbon dioxide, inert, or other low activity gases. The type of gas found in the bubbles generally is dictated by the types of aerogels that are commercially available. Ultra-light aerogels may be produced using helium as the gas. The aerogels do compress, but in contrast to hollow spheres, aerogels tend to resist crushing and/or breakage . Without limiting the invention to a particular mechanism of action, it is believed that fluid in the system moves into the bubble matrix under compression, giving the aerogel strength to resist breakage. Upon decompression, the fluid moves back out into the system fluid. The aerogels are stable at temperatures of 150 °C or more, preferably about 250 °C or more, more preferably about 350 °C or more, even more preferably about 450 °C, and most preferably 600 °C or more.
A most preferred aerogel is NANOGEL® manufactured by Cabot 5 Corporation, Boston, MA. Other suppliers of suitable aerogels include, but are not necessarily limited to NanoPore Inc., of Albuquerque, N.M.; Aspen Aerogels Inc., of Marlborough, Ma.; and Taasi Corporation, of Delaware, OH.
Silicon (silicate) based inorganic aerogels are normally produced either on a basis of water glass or acids as the raw material. Suitable processes for l o producing silica aerogels include, but are not necessarily limited to those described in U.S. Pat. No. 3,122,520; U.S. Patent No. 6,481,649; U.S. Patent No. 6,479,416; U.S. Patent No. 6,475,561; WO 94/25149; WO 92/20623, all of which are incorporated herein by reference.
Generally, the quantity of aerogel used in a system fluid will be 15 sufficient to produce a system fluid having a density of from about 1 lb/gal to about 8 lb/gal, preferably from about 3 lb/gal to about 6 lb/gal. The amount of aerogel required to achieve such reduced density will depend upon the type of aerogel and the "initial density" of the fluid in the absence of the aerogel.
As an example, to reduce the density of a given amount of water by one- 20 half, say from 8.5 to 4.25 lb/gal, using 0.1 to 0.2 specific gravity aerogels, the final volume of the resulting mixture will be from about 0.55 to 0.62% aerogel. Put another way, in order to prepare 100 bbls of a 4.25 lb/gal under-balanced fluid from an 8.5 lb/gal initial fluid requires inclusion of an amount of aerogel of from about 55 to about 62% of the final mix. The precise percentage will vary with the specific gravity of the aerogel used. Take the situation where the aerogel is NANOGEL®. The amount of NANOGEL® required to produce a fluid having a density of 6 lb/gal from an initial fluid having a density of 8 lb/gal is about 24 lb/bbl, and the amount of NANOGEL® required to produce a fluid having a density of about 4 lb/gal is about 48 lb/bbl.
Aerogels may be either hydrophilic or hydrophobic, depending on the process used in their construction and their composition. For example, alcohol dried aerogels generally have sealed pores which are impervious to water. Carbon dioxide dried aerogels generally are hydrophilic. Hydrophilic aerogels are preferred for use in relatively hydrophilic systems, such as water-based systems. Hydrophobic aerogels are preferred for use in relatively hydrophobic systems, such as oil-base systems. However, it is possible to disperse a hydrophobic aerogel in a hydrophilic system, or to disperse a relatively hydrophilic aerogel in a hydrophobic system, by first mixing the aerogel with a suitable surfactant. In a preferred embodiment, a hydrophilic aerogel is used such that a combination of heat, moderate pH (from about 8 to about 13), and contact with water converts the hydrophilic aerogel back to a silicone gel. The collapse of the aerogel structure permits hole clean up without the need to use corrosive acids. The residue of the filter cake may be collected using completion screens or gravel packs. The system fluid in which the aerogel is used may be water-based or oil- based. The phrase "water-based" includes any system fluid comprising water or a water-based solution as the continuous phase, including oil-in-water and oil- in-brine emulsions. The system fluids of the present application also may be oil based. The phrase "oil-based" includes system fluids comprising an organic material as a continuous phase, including water-in-oil and brine-in-oil emulsions, also sometimes called "invert emulsions."
Examples of suitable organic materials for the "oil" of such system fluids include but are not necessarily limited to olefins, paraffins, water insoluble polyglycols, water insoluble esters, diesel, water insoluble Fischer-Tropsch reaction products, and other organic materials , preferably materials that are non- toxic at the concentrations used, and combinations thereof. Suitable olefins are branched and/or linear and preferably are relatively non-toxic synthetic olefins. Examples of preferred olefins include but are not necessarily limited to polyalphaolefins, linear alpha olefins, and internal olefins, typically skeletally isomerized olefins. Most preferred olefins are described in U.S. Patent Nos. 5,605,872 and 5,851,958, incorporated herein by reference. Preferred paraffins are described in U.S. Patent No. 5,837,655, incorporated herein by reference.
The "oil" and other components used in the system fluid preferably are non-toxic. As used herein, the term "non-toxic" is defined to mean that a material meets the applicable EPA requirements for discharge into U.S. waters. Currently, a drilling fluid must have an LC5o (lethal concentration where 50% of the organisms are killed) of 30,000 parts per million (ppm) suspended particulate phase (SPP) or higher to meet the EPA standards. Preferred system fluids meet relevant environmental standards in the location of the operation. In order to be effective for use during drilling operations, the particular system fluid must have effective rheology and lubricity properties, and for near balanced and over-balanced drilling, effective fluid loss control properties. Viscosity preferably is controlled in the reduced density system fluids by adding certain polymers to the fluid. The system fluid preferably contains polymers that are capable of viscosifying the drilling system fluid and/or providing filtration control for the drilling system fluid. Preferred polymers are non-toxic and will depend upon the base fluid. Suitable polymers include, but are not necessarily limited to water soluble starches and modified versions thereof, water soluble polysaccharides and modified versions thereof, water soluble celluloses and modified versions thereof, and water soluble polyacrylamides and copolymers thereof. Generally, the quantity of polymer used is at least about 2 lb/bbl. or more, preferably about 7.5 lb/bbl. or more. Starches that are suitable for use in the system fluids include, but are not necessarily limited to corn based and potato based starches, preferred starches being more temperature stable starches. Polysaccharides that are suitable for use in the system fluids including, but not necessarily limited to xanthan polysaccharides, wellan polysaccharides, scleroglucan polysaccharides, and guar polysaccharides. Celluloses that are suitable for use in the system fluids include, but are not necessarily limited to hydrophobically modified hydroxyethyl celluloses and cationic cellulose ethers. Suitable copolymers of acrylamide include copolymers with acrylate monomers, hydrophobic N- isopropylacrylamide, and the like. As used herein, the terms "modified starches" and "modified polysaccharides" or "synthetically modified polysaccharides" refer to starches and polysaccharides that have been chemically modified in a manner that renders them inherently non-fermentable in order to avoid the need for a preservative. Water-soluble "modified starches" and "modified polysaccharides" that should operate successfully as water-soluble polymers include, but are not necessarily limited to: hydroxyalkyl starches and polysaccharides; starch and polysaccharide esters; cross-link starches and polysaccharides; hypochlorite oxidized starches and polysaccharides; starch and polysaccharide phosphate monoesters; cationic starches and polysaccharides; starch and polysaccharide xanthates; and, dialdehyde starches and polysaccharides. These derivatized starches and polysaccharides can be manufactured using known means, such as those set forth in detail in Chapter X of Starch: Chemistry and Technology 311-388 (Roy L. Whistler, et al. eds., 1984), incorporated herein by reference.
Specific examples of suitable modified starches and modified polysaccharides include, but are not necessarily limited to: carboxymethyl starches and polysaccharides; hydroxyethyl starches and polysaccharides; hydroxypropyl starches and polysaccharides; hydroxybutyl starches and polysaccharides; carboxymethylhydroxyethyl starches and polysaccharides; carboxymethylhydroxypropyl starches and polysaccharides; carboxymethylhydroxybutyl starches and polysaccharides; epichlorohydrin starches and polysaccharides; alkylene glycol modified starches and polysaccharides; and, other starch and polysaccharide copolymers having similar characteristics. Preferred modified starches and/or modified polysaccharides comprise a functional group selected from the group consisting of a carboxymethyl group, a propylene glycol group, and an epichlorohydrin group.
Where the system fluid is water-based, preferred viscosifiers and filtration control agents are biopolymers, including but not necessarily limited to XAN- PLEX™ D, BIO-PAQ™ and/or BIOLOSE™, all of which are commercially available from Baker Hughes INTEQ.
Where the system fluid is oil-base, preferred viscosifiers are organophilic clays and preferred filtration control agents are asphaltic and lignitic materials.
The viscosity of a fluid is its internal resistance to flow as measured in centipoise units. The coefficient of viscosity of a normal homogeneous fluid at a given temperature and pressure is a constant for that fluid and independent of the rate of shear or the velocity gradient. Fluids that obey this rule are "Newtonian" fluids. In fluids called "non-Newtonian fluids," this coefficient is not constant but is a function of the rate at which the fluid is sheared as well as of the relative concentration of the phases. Drilling fluids generally are non-Newtonian fluids. Non-Newtonian fluids frequently exhibit plastic flow, in which the flowing behavior of the material occurs after the applied stress reaches a critical value or yield point (YP). Yield points in drilling fluids are frequently expressed in units of pounds per square 100 feet, wherein the yield point is a function of the internal structure of the fluid.
In drilling, once the critical value or yield point (YP) of the drilling fluid is achieved, the rate of flow or rate of shear typically increases with an increase in pressure, causing flow or shearing stress. The rate of flow change, known as plastic viscosity (PV), is analogous to viscosity in Newtonian fluids and is similarly measured in centipoise units. In drilling fluids, yield points (YP) above a minimum value are desirable to adequately suspend solids, such as weighting agents and cuttings. The fluid preferably has a yield point of from about 20 to about 50, preferably 30 or more pounds per 100 square feet.
Conventional additives may be used in the fluid. Such additives include, but are not necessarily limited to shale stabilizer(s), filtration control additive(s), 5 suspending agent(s), dispersant(s), thinner(s), anti-balling additive(s), lubricant(s), weighting agent(s), seepage control additive(s), lost circulation additive(s), drilling enhancer(s), penetration rate enhancer(s), corrosion inhibitor(s), acid(s), base(s), buffer(s), scavenger(s), gelling agent(s), cross- linkers), catalyst(s), soluble salts, biocides; one or more bridging and/or 0 weighting agents may be added to the fluid, and combinations thereof. Suitable shale stabilizers include, but are not necessarily limited to polyglycols, inorganic salts, chelates, amines, alkanolamines, alkanolamides, amphoteric compounds, alone or in aqueous solutions, and mixtures thereof. Suitable shale stabilizing inorganic salts include, but are not necessarily limited to alkali metal 5 salts, silicate salts, and aluminum salts. Acids include acids used to treat cement contamination.
Preferred systems for use with the aerogels are PERFFLOW® and SCIFLOW™, which are commercially available from Baker Hughes INTEQ, Houston, Texas. o The fluid is prepared using conventional procedures. It may be desirable to use injection , induction, and/or shear in order to achieve adequate mixing. The pH of the fluid is measured and, if needed, adjusted to from about 8.5 to about 11.5, preferably about 9.5. The pH preferably is adjusted using a suitable organic base as a buffer. Substantially any buffer may be used. Suitable buffers include, but are not necessarily limited to ethanolamines (preferably triethanolamines), alkali metal hydroxides, preferably sodium or potassium hydroxide, alkali metal acetates, preferably sodium or potassium acetate. Preferred buffers are alkali metal oxides, most preferably magnesium oxide.
The application will be better understood with reference to the following examples, which are illustrative only:
Example 1
A fluid was prepared having the following composition:
Figure imgf000017_0001
The rheological and HPHT/PPA filtration control properties were measured using standard procedures with the following results:
Figure imgf000017_0002
The fluid demonstrated low density and suitable rheological and filtration control properties.
Example 2 A fluid was prepared having the following composition:
Figure imgf000018_0001
The rheological and HPHT/PPA filtration control properties were l o measured using standard procedures with the following results:
15
Figure imgf000018_0002
20
Persons of ordinary skill in the art will recognize that many modifications may be made to the present application without departing from the spirit and scope of the application. The embodiment described herein is meant to be illustrative only and should not be taken as limiting the application, which is defined in the claims.

Claims

We claim:
1. A system fluid having effective rheology comprising an amount of one or more aerogels effective to reduce density of said system fluid compared to the same system fluid absent said amount of said one or more aerogels.
2. The system fluid of claim 1 selected from the group consisting of drilling fluids, drill-in fluids, completion fluids, workover fluids, spotting fluids, and cementing fluids.
3. The system fluid of claim 1 comprising a drilling system fluid selected from the group consisting of drilling fluids, drill-in fluids, completion fluids, workover fluids, and spotting fluids.
4. The system fluid of claims 1-2 and 3 wherein said one or more aerogels comprise one or more inorganic aerogels.
5. The system fluid of claims 1-2 and 3 wherein said one or more aerogels comprise one or more organic aerogels.
6. The system fluid of claims 1-4 and 5 wherein said one or more aerogels are hydrophilic.
7. The system fluid of claim 1-5 and 6 wherein said one or more aerogels comprise an element selected from the group consisting of silicon, aluminum, titanium, zirconium, tin, lithium, cerium, vanadium, and mixtures thereof.
8. The system fluid of claims 1-6 and 7 wherein said one or more aerogels comprise silicon.
9. The system fluid of claims 1-7 and 8 wherein said one or more aerogels comprise silicon oxide.
10. The system fluid of claims 1-8 and 9 wherein said one or more aerogels comprise particles having an average diameter of about 200 μm or less.
11. The system fluid of claims 1 -9 and 10 wherein said one or more aerogels comprising particles having an average diameter of about 1 μm or more.
12. The system fluid of claims 1-8 and 9 wherein said one or more aerogels comprises particles having an average diameter of from about 1 μm to about 44 μm.
13. The system fluid of claims 1-11 and 12 wherein said one or more aerogels comprise particles having a particle size distribution effective to bridge pores in a subterranean formation.
14. The system fluid of claims 1-12 and 13 wherein said one or more aerogels comprise particles having a particle size distribution which produces an effective filter cake during drilling operations.
15. The system fluid of claims 1-13 and 14 wherein said one or more aerogels comprise particles having a density of about 0.2 g/cm3 or less.
16. The system fluid of claims 1-14 and 15 wherein said one or more aerogels comprise particles having a density of about 0.35 g/cm3 or less.
17. The system fluid of claims 1-13 and 14 wherein said one or more aerogels comprise particles having a density of from about 0.1 to about 0.35 g/cm3.
18. The system fluid of claims 1-16 and 17 wherein said one or more aerogels comprise particles comprising about 90% gas or more.
19. The system fluid of claims 1-16 and 17 wherein said one or more aerogels comprises particles comprising about 95%> gas or more.
20. The system fluid of claims 1-18 and 19 wherein said one or more aerogels comprise particles having a total surface area of about 200 m2/g or more.
21. The system fluid of claims 1-18 and 19 wherein said one or more aerogels comprise particles having a total surface area of about 600 m2/g or more.
22. The system fluid of claims 1-18 and 19 wherein said one or more aerogels comprise particles having a total surface area of about 700 m2/g or more.
23. The system fluid of claims 1-21 and 22 wherein said one or more aerogels comprise particles comprising a bubble matrix comprising retained gas selected from the group consisting of air, oxygen, helium, nitrogen, carbon dioxide, and inert or low activity gases.
24. The system fluid of claims 1-21 and 22 wherein said one or more aerogels comprise particles comprising a bubble matrix comprising retained air.
25. The system fluid of claims 1-21 and 22 wherein said one or more aerogels comprises particles comprising a bubble matrix comprising retained helium.
26. The system fluid of claims 1 -24 and 25 wherein said one or more aerogels are stable at temperatures of about 150 °C or more.
27. The system fluid of claims 1-24 and 25 wherein said one or more aerogels are stable at temperatures of about 250 °C or more.
28. The system fluid of claims 1-24 and 25 wherein said one or more aerogels are stable at temperatures of about 350 °C or more.
29. The system fluid of claims 1-24 and 25 wherein said one or more aerogels are stable at temperatures of about 450 °C. or more.
30. The system fluid of claims 1-24 and 25 wherein said one or more aerogels are stable at temperatures of about 600 °C or more.
31. The system fluid of claims 1 -29 and 30 wherein said one or more aerogels comprise NANOGEL .
32. The system fluid of claims 1-30 and 31 wherein said amount of said one or more aerogels produces a system fluid density of from about 1 lb/gal to about 8 lb/gal.
33. The system fluid of claims 1-30 and 31 wherein said amount of said one or more aerogels produces a system fluid density of from about 3 lb/gal to about 6 lb/gal.
34. The system fluid of claims 1-32 and 33 wherein said system fluid is hydrophilic and said one or more aerogels are hydrophilic.
35. The system fluid of claims 1-32 and 33 wherein said system fluid is hydrophobic and said one or more aerogels are hydrophobic.
36. The system fluid of claims 1-34 and 35 wherein a filter cake comprising said one or more aerogels is converted to a gel upon exposure to one or more component selected from the group consisting of heat, a pH of from about 8 to about 13, and contact with water.
37. The system fluid of claims 1-35 and 36 wherein a borehole comprising a filter cake comprising said one or more aerogels is cleaned in the absence of acid.
38. The system fluid of claims 1-36 and 37 wherein said system fluid is selected from the group consisting of water-based and oil-based fluid.
39. The system fluid of claims 1-37 and 38 wherein said system fluid comprises an oil selected from the group consisting of olefins, paraffins, water insoluble polyglycols, water insoluble esters, diesel, water insoluble Fischer- Tropsch reaction products, other organic materials that are non-toxic at the concentrations used, and combinations thereof.
40. The system fluid of claims 1-37 and 38 wherein said system fluid comprises one or more non-toxic synthetic olefins.
41. The system fluid of claims 1-37 and 38 wherein said system fluid comprises one or more non-toxic olefins selected from the group consisting of polyalphaolefins, linear alpha olefins, and internal olefins.
42. The system fluid of claims 1-37 and 38 wherein said system fluid is selected from the group consisting of PERFFLOW® and SCIFLOW™.
43. The system fluid of claims 1-41 and 42 wherein the amount of said one or more aerogels produces a system fluid density of from about 1 lb/gal to about 8 lb/gal.
44. The system fluid of claims 1-41 and 42 wherein the amount of said one or more aerogels produces a system fluid density of from about 3 lb/gal to about 6 lb/gal.
45. The system fluid of claims 1-43 and 44 wherein said amount of 2 said one or more aerogels is from about 55 to about 62% of said system fluid.
3
1 46. A method comprising using the system fluid of any of claims 1-
2 44 and 45 during drilling operations. i 47. The method of claim 46 further comprising effectively bridging
2 pores in a formation during said drilling operations with a bridging agent
3 comprising said one or more aerogels. i 48. The method of claims 46 and 47 further comprising producing an
2 effective filter cake comprising said one or more aerogels during said drilling
3 operations.
1 49. The method of claim 48 further comprising converting said filter
2 cake to a gel upon exposure to one or more component selected from the group
3 consisting of heat, a pH of from about 8 to about 13, and contact with water. i 50. The method of claim 48 further comprising effectively cleaning a
2 borehole comprising said filter cake in the absence of acid.
1 51. A method for reducing density of fluids useful during drilling
2 operations comprising providing a quantity of a system fluid comprising an
3 amount of one or more aerogels, the system fluid having effective rheology and
4 lubricity properties and having a reduced density compared to the same system
5 fluid absent said amount of said one or more aerogels.
1 52. The method of claim 51 wherein said system fluid is selected
2 from the group consisting of drilling fluids, drill-in fluids, completion fluids,
3 workover fluids, spotting fluids, and cementing fluids. l 53. The method of claim 51 wherein said system fluid is a drilling 2 system fluid selected from the group consisting of drilling fluids, drill-in fluids,
3 completion fluids, workover fluids, and spotting fluids.
1 54. The method of claims 51-52 and 53 further comprising effectively bridging pores in a formation during said drilling operations using a
3 bridging agent comprising said one or more aerogels.
1 55. The method of claims 51-53 and 54 further comprising
2 producing an effective filter cake comprising said one or more aerogels during
3 said drilling operations.
1 56. The method of claims 51-54 and 55 wherein said amount of said
2 one or more aerogels is effective to produce a system fluid density of from
3 about 1 lb/gal to about 8 lb/gal. l. 57. The method of claims 51-54 and 55 wherein said amount of said
2 one or more aerogels is effective to produce a system fluid density of from
3 about 3 lb/gal to about 6 lb/gal. i 58. The method of claims 55-56 and 57 further comprising
2 converting said filter cake to a gel upon exposure to one or more component
3 selected from the group consisting of heat, a pH of from about 8 to about 13, and contact with water.
1 59. The method of claims 55-56 and 57 further comprising cleaning
2 a borehole comprising said filter cake in the absence of acid.
1 60. The system fluid of claims 51-58 and 59 wherein said amount of
2 said one or more aerogels is from about 55 to about 62% of said system fluid.
PCT/US2003/041734 2002-12-31 2003-12-31 Aerogels effective to reduce drilling fluid density WO2004061046A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003300150A AU2003300150A1 (en) 2002-12-31 2003-12-31 Aerogels effective to reduce drilling fluid density

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US43730502P 2002-12-31 2002-12-31
US60/437,305 2002-12-31

Publications (2)

Publication Number Publication Date
WO2004061046A1 true WO2004061046A1 (en) 2004-07-22
WO2004061046B1 WO2004061046B1 (en) 2004-09-23

Family

ID=32713165

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/041734 WO2004061046A1 (en) 2002-12-31 2003-12-31 Aerogels effective to reduce drilling fluid density

Country Status (3)

Country Link
US (2) US8034749B2 (en)
AU (1) AU2003300150A1 (en)
WO (1) WO2004061046A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018222958A3 (en) * 2017-06-02 2019-01-10 Saudi Arabian Oil Company Low-density gels and composites for protecting underground electric components from chemical damage
US11230661B2 (en) 2019-09-05 2022-01-25 Saudi Arabian Oil Company Propping open hydraulic fractures
US11326092B2 (en) 2020-08-24 2022-05-10 Saudi Arabian Oil Company High temperature cross-linked fracturing fluids with reduced friction
US11680201B1 (en) 2022-03-31 2023-06-20 Saudi Arabian Oil Company Systems and methods in which colloidal silica gel is used to seal a leak in or near a packer disposed in a tubing-casing annulus
US11891564B2 (en) 2022-03-31 2024-02-06 Saudi Arabian Oil Company Systems and methods in which colloidal silica gel is used to resist corrosion of a wellhead component in a well cellar

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8034749B2 (en) * 2002-12-31 2011-10-11 Baker Hughes Incorporated Aerogels effective to reduce drilling fluid density
EP2813664B1 (en) 2005-10-20 2018-08-22 Transocean Sedco Forex Ventures Ltd. Apparatus and method for managed pressure drilling
US20090140444A1 (en) * 2007-11-29 2009-06-04 Total Separation Solutions, Llc Compressed gas system useful for producing light weight drilling fluids
US20090188721A1 (en) * 2008-01-30 2009-07-30 Smith Kevin W Membrane method of making drilling fluids containing microbubbles
US20120186877A1 (en) * 2010-08-13 2012-07-26 Ezell Ryan G Modified Cellulosic Polymer for Improved Well Bore Fluids
US20130149549A1 (en) * 2011-12-12 2013-06-13 Nicholas Francis Borrelli Metallic structures by metallothermal reduction
EP2867325A1 (en) * 2012-06-29 2015-05-06 Baker Hughes Incorporated Low-density downhole fluids and uses therof
US10858570B2 (en) * 2012-07-17 2020-12-08 Dow Global Technologies Llc Aqueous cement compositions incorporating particles that are activated to control rheology when water soluble portions of the particles are released in the presence of water
WO2015112186A1 (en) * 2014-01-21 2015-07-30 Baker Hughes Incorporated Method of improving cleanout of a wellbore
CA3125298A1 (en) 2019-07-01 2021-01-07 Highland Fluid Technology, Inc. Managed pressure drilling with noncompressible light weight fluid
WO2022005962A1 (en) * 2020-06-29 2022-01-06 Saudi Arabian Oil Company Low-density treatment fluid and methods for treating thief zones located above pay zones

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2455188A (en) * 1946-02-25 1948-11-30 Sun Oil Co Drilling fluid
GB1171409A (en) * 1966-06-15 1969-11-19 Cabot Corp Siliceous Rheological Agents
US3951824A (en) * 1973-02-12 1976-04-20 Continental Oil Company Dry drilling fluid composition
EP0786507A1 (en) * 1995-08-08 1997-07-30 Texas United Chemical Company, Llc. Brine fluids having improved rheological characteristics

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2093454A (en) * 1934-10-01 1937-09-21 Samuel S Kistler Method of producing aerogels
US2109337A (en) * 1935-09-09 1938-02-22 Corona Products Inc Amorphous silica drilling fluid
US2584085A (en) * 1948-07-20 1952-01-29 Shell Dev Lubricant
US3122520A (en) * 1959-10-05 1964-02-25 Dow Corning Method of making silicone rubber fillers
US5350395A (en) * 1986-04-15 1994-09-27 Yock Paul G Angioplasty apparatus facilitating rapid exchanges
NO912006D0 (en) 1991-05-24 1991-05-24 Sinvent As PROCEDURE FOR THE MANUFACTURE OF A SILICA-AEROGEL-LIKE MATERIAL.
US5565142A (en) 1992-04-01 1996-10-15 Deshpande; Ravindra Preparation of high porosity xerogels by chemical surface modification.
US5527753A (en) * 1994-12-13 1996-06-18 Fmc Corporation Functionalized amine initiators for anionic polymerization
US5501277A (en) * 1995-03-06 1996-03-26 Halliburton Company Combating lost circulation during the drilling of wells
US5605879A (en) * 1995-04-17 1997-02-25 Baker Hughes Incorporated Olefin isomers as lubricants, rate of penetration enhancers, and spotting fluid additives for water-based drilling fluids
US5728654A (en) * 1995-08-25 1998-03-17 Texas United Chemical Company, Llc. Stabilized fluids containing soluble zinc
DE19548128A1 (en) * 1995-12-21 1997-06-26 Hoechst Ag Nonwoven airgel composite material containing at least one thermoplastic fiber material, process for its production and its use
US5837655A (en) * 1996-05-01 1998-11-17 Halliday; William S. Purified paraffins as lubricants, rate of penetration enhancers, and spotting fluid additives for water-based drilling fluids
DE19718740A1 (en) * 1997-05-02 1998-11-05 Hoechst Ag Process for the granulation of aerogels
DE19752456A1 (en) * 1997-11-26 1999-05-27 Hoechst Ag Production of organically modified silica aerogel
US6131661A (en) * 1998-08-03 2000-10-17 Tetra Technologies Inc. Method for removing filtercake
JP3414652B2 (en) * 1998-10-12 2003-06-09 敷島製パン株式会社 Wheat flour baked product, its production method and quality improving agent
BR0304524B1 (en) * 2002-04-16 2015-02-10 Texas United Chemical Corp OIL-BASED WELL DRILLING AND MAINTENANCE FLUID
US8034749B2 (en) * 2002-12-31 2011-10-11 Baker Hughes Incorporated Aerogels effective to reduce drilling fluid density

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2455188A (en) * 1946-02-25 1948-11-30 Sun Oil Co Drilling fluid
GB1171409A (en) * 1966-06-15 1969-11-19 Cabot Corp Siliceous Rheological Agents
US3951824A (en) * 1973-02-12 1976-04-20 Continental Oil Company Dry drilling fluid composition
EP0786507A1 (en) * 1995-08-08 1997-07-30 Texas United Chemical Company, Llc. Brine fluids having improved rheological characteristics

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LEE K-H ET AL: "LOW-DENSITY, HYDROPHOBIC AEROGELS", JOURNAL OF NON-CRYSTALLINE SOLIDS, NORTH-HOLLAND PHYSICS PUBLISHING. AMSTERDAM, NL, vol. 186, 15 June 1995 (1995-06-15), pages 18 - 22, XP000683679, ISSN: 0022-3093 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018222958A3 (en) * 2017-06-02 2019-01-10 Saudi Arabian Oil Company Low-density gels and composites for protecting underground electric components from chemical damage
CN110869463A (en) * 2017-06-02 2020-03-06 沙特阿拉伯石油公司 Low density gels and composites for protecting underground electrical components from chemical damage
JP2020522587A (en) * 2017-06-02 2020-07-30 サウジ アラビアン オイル カンパニー Low density gels and composites to protect underground electrical components from chemical damage
US11230661B2 (en) 2019-09-05 2022-01-25 Saudi Arabian Oil Company Propping open hydraulic fractures
US11326092B2 (en) 2020-08-24 2022-05-10 Saudi Arabian Oil Company High temperature cross-linked fracturing fluids with reduced friction
US11680201B1 (en) 2022-03-31 2023-06-20 Saudi Arabian Oil Company Systems and methods in which colloidal silica gel is used to seal a leak in or near a packer disposed in a tubing-casing annulus
US11891564B2 (en) 2022-03-31 2024-02-06 Saudi Arabian Oil Company Systems and methods in which colloidal silica gel is used to resist corrosion of a wellhead component in a well cellar

Also Published As

Publication number Publication date
AU2003300150A1 (en) 2004-07-29
WO2004061046B1 (en) 2004-09-23
US20040147405A1 (en) 2004-07-29
US20070056731A1 (en) 2007-03-15
US8034749B2 (en) 2011-10-11
US7303013B2 (en) 2007-12-04

Similar Documents

Publication Publication Date Title
US7303013B2 (en) Method for reducing density of a system fluid and for performing drilling operations using a reduced density system fluid comprising aerogel
US7148183B2 (en) Surfactant-polymer composition for substantially solid-free water based drilling, drill-in, and completion fluids
CA2521749C (en) Drilling fluids comprising sized graphite particles
US5706895A (en) Polymer enhanced foam workover, completion, and kill fluids
US8739876B2 (en) Nanohybrid-stabilized emulsions and methods of use in oil field applications
AU2016413727B2 (en) Treatment fluids comprising recycled drilling cuttings and methods of use
EP2038362B1 (en) Fluid loss additive for oil-based muds
Ismail Improve performance of water-based drilling fluids
CA2515058C (en) Stabilized colloidal and colloidal-like systems
EP1435428A2 (en) Plugging depleted downhole sands
EP1128021B1 (en) Solids-free viscous fluids
US20060122070A1 (en) Drilling fluid systems comprising sized graphite particles
US7977281B2 (en) Methods for minimizing the amount of graphite particles used during drilling operations
WO2020106272A1 (en) High temperature treatment fluid with nanocellulose
CA2515060C (en) Stabilized colloidal and colloidal-like systems
NO20210469A1 (en) Low density oil-based wellbore fluids and methods thereof
EP1892278A1 (en) Drilling fluids comprising sized graphite particles
US20230203361A1 (en) Wellbore stability compositions comprising nanoparticles

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SK SL TJ TM TR TT UA UG UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
B Later publication of amended claims

Effective date: 20040803

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP