CA2505045C - Organofunctional compounds for shale stabilization of the aqueous dispersed phase of non-aqueous based invert emulsion drilling system fluids - Google Patents
Organofunctional compounds for shale stabilization of the aqueous dispersed phase of non-aqueous based invert emulsion drilling system fluids Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
- C09K8/34—Organic liquids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
- C09K8/36—Water-in-oil emulsions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
- C09K8/48—Density increasing or weighting additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
- C09K8/487—Fluid loss control additives; Additives for reducing or preventing circulation loss
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
- C09K8/76—Eroding chemicals, e.g. acids combined with additives added for specific purposes for preventing or reducing fluid loss
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
Abstract
Invert emulsion drilling system fluids comprising an oleaginous continuous phase and a non-oleaginous dispersed phase, the dispersed phase comprising organofunctional compounds(s) effective to provide shale inhibition. The organofunctional compound(s) may be used either as a supplement to or as a substitute for metallic salts.
Description
ORGANOFUNCTIONAL COMPOUNDS FOR SHALE STABILIZATION OF
THE AQUEOUS DISPERSED PHASE OF NON-AQUEOUS
BASED INVERT EMULSION DRILLING SYSTEM FLUIDS
Field of the Invention [0001] The invention relates to invert emulsion drilling system fluids. More particularly, the invention relates to invert emulsion drilling system fluids comprising an oleaginous continuous phase and a non-oleaginous dispersed phase, the dispersed phase comprising organofunctional compounds) effective to provide shale inhibition.
The organofunctional compounds) may be used either as a supplement to or as a substitute for metallic salts.
Background of the Invention [0002] Drilling system fluids comprising water as the continuous phase often are ecologically favored over fluids in which oil is the continuous phase.
Unfortunately, the walls of a wellbore frequently are composed, at least in part, of shale.
When exposed to water, many shales swell, Slough, or spall to the extent that they prevent further operation of the wellbore. Shale also may Slough during gravel transport in open-hole completion, mix with the gravel, and/or reduce the productivity of the well by choking off the permeability of the gravel pack. Shale sloughing also may cause screen blinding.
THE AQUEOUS DISPERSED PHASE OF NON-AQUEOUS
BASED INVERT EMULSION DRILLING SYSTEM FLUIDS
Field of the Invention [0001] The invention relates to invert emulsion drilling system fluids. More particularly, the invention relates to invert emulsion drilling system fluids comprising an oleaginous continuous phase and a non-oleaginous dispersed phase, the dispersed phase comprising organofunctional compounds) effective to provide shale inhibition.
The organofunctional compounds) may be used either as a supplement to or as a substitute for metallic salts.
Background of the Invention [0002] Drilling system fluids comprising water as the continuous phase often are ecologically favored over fluids in which oil is the continuous phase.
Unfortunately, the walls of a wellbore frequently are composed, at least in part, of shale.
When exposed to water, many shales swell, Slough, or spall to the extent that they prevent further operation of the wellbore. Shale also may Slough during gravel transport in open-hole completion, mix with the gravel, and/or reduce the productivity of the well by choking off the permeability of the gravel pack. Shale sloughing also may cause screen blinding.
[0003] The use of invert emulsion drilling system fluids may help to minimize shale hydration. An invert emulsion fluid comprises "oil" as the continuous phase and an emulsified aqueous dispersed phase. In order to minimize hydration of shale, the aqueous dispersed phase typically comprises a brine comprising metallic salts at a salinity greater than the salinity of the interstitial water in the shale.
[0004] Unfortunately, contamination by highly reactive drilled solids may cause rheological and/or filtration control problems and also may decrease emulsion stability in invert emulsion drilling system fluids. Alternative invert emulsion drilling system fluids are needed.
Summary [0005] An invert emulsion drilling system fluid with effective rheology and fluid loss control properties, said drilling system fluid comprising an oleaginous continuous phase and a non-oleaginous dispersed phase, said dispersed phase comprising an amount of at least one organofunctional compound effective to provide shale inhibition.
Brief Description of Figure [0006] Fig. 1 is a Table giving the components used and the results obtained in Example 3.
Detailed Description [0007] The present application provides invert emulsion drilling system fluids which are effective to minimize shale hydration by the dispersed phase while maintaining effective rheology, filtration control, and emulsion stability in the presence of contamination by reactive drilled solids. The invert emulsion drilling system fluids avoid the need to use high concentrations of metallic salts in order to achieve shale stabilization.
Summary [0005] An invert emulsion drilling system fluid with effective rheology and fluid loss control properties, said drilling system fluid comprising an oleaginous continuous phase and a non-oleaginous dispersed phase, said dispersed phase comprising an amount of at least one organofunctional compound effective to provide shale inhibition.
Brief Description of Figure [0006] Fig. 1 is a Table giving the components used and the results obtained in Example 3.
Detailed Description [0007] The present application provides invert emulsion drilling system fluids which are effective to minimize shale hydration by the dispersed phase while maintaining effective rheology, filtration control, and emulsion stability in the presence of contamination by reactive drilled solids. The invert emulsion drilling system fluids avoid the need to use high concentrations of metallic salts in order to achieve shale stabilization.
[0008] The invert emulsion drilling system fluids comprise a continuous phase comprising an "oleaginous" liquid and a dispersed phase comprising a "non-oleaginous" liquid. As used herein, the term "oleaginous liquid" means an oil which is immiscible with water and exists as a liquid at 25 °C. The oleaginous liquid preferably is 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 LCso (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.
waters.
Currently, a drilling fluid must have an LCso (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.
[0009] Suitable oleaginous liquids include, but are not necessarily limited to olefins, paraffms, water insoluble polyglycols, water insoluble esters, water insoluble Fischer-Tropsch reaction products, and other non-toxic organic materials, and combinations thereof. Suitable paraffins are described in U.S. Patent No. 5,837,655, incorporated herein by reference. Suitable polyglycols have a molecular weight sufficiently high to render them water insoluble.
[0010] Preferred oleaginous liquids are relatively non-toxic branched and/or linear a olefins. Examples of suitable olefins include, but are not necessarily limited to polyalphaoleflns, linear alpha olefins, and internal olefins, preferably skeletally, isomerized olefins, and mixtures thereof. Preferred olefins are described in U.S.
Patent Nos. 5,605,879 and 5,851,958, incorporated herein by reference. In a preferred embodiment, the oleaginous phase comprises olefins having at least 14 carbon atoms, more preferably at least 15 carbon atoms, and most preferably at least 16 carbon atoms. In a most preferred embodiment, the oleaginous phase is C16, C18 isomerized olefins, which are available from Chevron Phillips Chemical Company.
Patent Nos. 5,605,879 and 5,851,958, incorporated herein by reference. In a preferred embodiment, the oleaginous phase comprises olefins having at least 14 carbon atoms, more preferably at least 15 carbon atoms, and most preferably at least 16 carbon atoms. In a most preferred embodiment, the oleaginous phase is C16, C18 isomerized olefins, which are available from Chevron Phillips Chemical Company.
[0011] The amount of oleaginous liquid, preferably olefins, in the invert emulsion fluid varies depending upon the particular oleaginous liquid used, the non-oleaginous liquid used, and the particular application in which the invert emulsion fluid is to be employed. The amount of oleaginous liquid generally is sufficient to form the continuous phase and for the non-oleaginous liquid to form a stable emulsion in the oleaginous liquid. The quantity of oleaginous liquid will increase with the density of a given fluid. Typically, the amount of oleaginous liquid is at least about 50 vol.% of the total invert emulsion fluid.
[0012] As used herein, the term "non-oleaginous liquid" means a material which is a liquid at 25 °C. and which is not an oleaginous liquid, as defined above. Non-oleaginous liquids are immiscible with the oleaginous liquid, and form an emulsion in the oleaginous liquid which preferably is stabilized by a suitable emulsifier.
Suitable non-oleaginous liquids include aqueous substances such as water, seawater, and/or brine comprising inorganic or organic dissolved salts, as well as water-miscible organic compounds. A most preferred non-oleaginous liquid is seawater.
Suitable non-oleaginous liquids include aqueous substances such as water, seawater, and/or brine comprising inorganic or organic dissolved salts, as well as water-miscible organic compounds. A most preferred non-oleaginous liquid is seawater.
[0013] The drilling system fluids are useful in rotary drilling processes for drilling subterranean formations containing oil, gas, or other minerals, and in geothermal drilling, water drilling, and geoscientific drilling. Invert emulsion drilling system fluids provide stability to the drilled hole (typically called the wellbore), form a thin filter cake, lubricate the wellbore, and often penetrate salt beds without undue sloughing or enlargement of the drilled hole. As used herein, the term "invert emulsion drilling system fluid" also encompasses spotting fluids, lubricating additives, and other additives used during drilling operations, and invert emulsions comprising such additives.
[0014] Preferred invert emulsion drilling system fluids for use herein are "drilling fluids" and "drill-in" fluids. A "drilling fluid" is used to drill a borehole through the earth to reach the payzone. 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.
[0015] In order to prevent bit balling and sloughing off of shale which comes into contact with the dispersed phase, it is necessary to provide shale stabilization. It is possible to provide shale stabilization by using a high concentration of inorganic salt in the dispersed phase. Clay chemistry has shown that cationic base exchange with the negatively charged clay minerals commonly found in shale formations, limits their ability to hydrate, soften, and swell, thereby rendering them more stable in the presence of water based fluids and reducing or preventing screen blinding.
Unfortunately, concentrated solutions of inorganic salts are toxic.
Unfortunately, concentrated solutions of inorganic salts are toxic.
[0016] The present application provides shale stabilization by providing the non-oleaginous phase with a quantity of at least one organofunctional compound comprising "exchangeable groups," defined as moieties which dissociate from the compound and exchange with water reactive sites present in surrounding clay or shale and reduce or preferably prevent screen blinding. Suitable exchangeable groups are electrophilic groups, most preferably cations. Without limiting the invention to particular theory or mechanism of action, it is believed that the exchangeable groups block water reactive sites in the clay, which prevents those sites from absorbing water, and thereby prevents swelling and/or sloughing of the clay or shale.
20' [0017] The exchangeable groups preferably are derived from primary functional groups. Most preferably, the organofunctional compound comprises at least two primary functional groups. By "primary functional groups" is meant a functional group which is bound to a single alkyl moiety. For example, an alkyl amine is a primary functional group. A dialkyl amine is not a primary functional group.
[0018] Examples of primary functional groups comprising suitable exchangeable groups include, but are not necessarily limited to nitrogen containing groups, oxygen containing groups, sulfur containing groups, and phosphorus containing groups.
Preferred primary functional groups are selected from the group consisting of amine groups, hydroxyl groups, and salts thereof. More preferred primary functional groups are selected from the group consisting of amine groups and salts thereof, preferably amine groups and protonated amine groups. Even more preferably, the organofunctional compound is selected from the group consisting of a diamine and salts thereof, most preferably an alkylenediamine wherein the alkyl moiety comprises from about 1 to about 7 to carbon atoms, preferably from about 2 to about 7 carbon atoms, and more preferably from about 2 to about 6 carbon atoms, wherein the carbon atoms may be joined to form a cycloalkyl.
[0019] Suitable organofunctional compounds for use in the dispersed phase have the following general structure:
x R Y
wherein X and Y independently are primary functional groups comprising exchangeable groups. Preferably, X and Y independently are selected from the group consisting of nitrogen containing groups, oxygen containing groups, sulfur containing groups, and phosphorus containing groups. More preferably X and Y independently are selected from the group consisting of amine groups, hydroxyl groups, and salts thereof; most preferably both X and Y
independently are selected from the group consisting of amine groups and salts thereof;
R is selected from the group consisting of linear alkylene groups having from about 1 to about 7 carbon atoms, preferably from about 2 to about 7 carbon atoms, most preferably from about 2 to about 6 carbon atoms, and cyclic alkylene groups having from about 3 to about 6 carbon atoms, wherein R is either unsubstituted or bears substituents effective to maintain or increase the dissociability of the exchangeable groups. For example, where the exchangeable group is cationic in nature, acceptable substituents either would not affect the charge distribution of the molecule or would be electrophilic or cationic in nature.
[0020] In a preferred embodiment, the organofunctional salt is selected from the group consisting of urea, alkanolamines, diaminocycloalkanes, substituted or unsubstituted alkylene diaminesand, combinations thereof. In a more preferred embodiment, the organic material is selected from the group consisting of substituted or unsubstituted trialkanolamines; diaminocycloalkanes; alkylene diamines;
and, combinations thereof. In a most preferred embodiment, the organofunctional compounds are selected from the group consisting of substituted or unsubstituted triethanolamines, diaminocyclohexanes, hexarnethylenediamines, salts thereof, and combinations thereof. A preferred commercially available mixture is CLAYTROLTM, which is commercially available from Baker Hughes INTEQ.
[0021] A given organofunctional compound is "effective to provide shale inhibition"
when the organofunctional compound produces an invert emulsion fluid that exhibits electrical stability of 350-450 volts and HTHP (high temperature high pressure differential filtration) of 6 or less.
[0022] The amount of non-oleaginous liquid in the invert emulsion fluid varies depending upon the particular non-oleaginous liquid used and the particular application in which the invert emulsion fluid is to be employed. The amount of non-. oleaginous liquid is effective to produce a stable emulsion and decreases with the density of the fluid. Typically, the amount of non-oleaginous liquid is at least about 1 vol.%, preferably from about 1 vol.% to about 50 vol.% or less of the total invert emulsion fluid.
[0023] The invert emulsions generally may comprise other components known in the art. Composition and Properties of Drilling and Completion Fluids, 5th Edition, H. C.
H. Darley, George R. Gray, Gulf Publishing Company, 1988, pp. 328-332, incorporated by reference. Conventional additives include, but are not necessarily limited to shale stabilizers) other than the organofunctional compound(s), filtration control additive(s), 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-linker(s), catalyst(s), soluble salts, biocides, and combinations thereof. Lime or another alkaline material may be added to an invert emulsion fluid to maintain a reserve alkalinity and to counter acidic gases, which often are encountered during drilling operations.
[0024] In a preferred embodiment, the invert emulsion fluid comprises:
emulsifier(s), clay(s), preferably quaternized clay(s), rheological modifier(s), preferably acrylate or methacrylate based modifier(s), weighting agent(s), and, wetting agents) effective to prevent fluid loss. A preferred type of wetting agent is a polyolefin amide alkene amine wetting agent, most preferably BIO-COTETM, available from Baker Hughes INTEQ.
[0025] Substantially any method may be used to prepare the invert emulsion drilling system fluids of the present invention as long as the method is effective to form an invert emulsion. Generally, the components are mixed together in any order under agitation conditions. In a preferred embodiment, an appropriate quantity of non-oleaginous liquid is mixed with an appropriate quantity of the organofunctional compound and, if necessary or desired, an acid to protonate the organofunctional compound. The resulting mixture is subjected to mild agitation. An oleaginous fluid is then added while mixing until an invert emulsion is formed. If a weight material is to be used, then the weight material typically is added after the invert emulsion fluid is formed.
[0026] One skilled in the art may readily identify whether the~appropriate ingredients and amounts have been used to form the invert emulsion using the following test:
Invert Emulsion Test [0027] A small portion of the emulsion is placed in a beaker which contains an oleaginous fluid. If the emulsion is an invert emulsion, the small portion will disperse in the oleaginous fluid. Visual inspection determines whether the small portion added has dispersed.
[0028] Alternately, the electrical stability of the invert emulsion is tested using known procedures. Generally, voltage is applied across two electrodes immersed in the emulsion, and the voltage is increased until the emulsion breaks and a surge of current flows between the two electrodes. The voltage required to break the emulsion is a common measure of the stability of an emulsion. Other tests are described on page 166 of the book, Composition and Properties of Drilling and Completion Fluids, 5th Edition, H. C. H. Darley and George Gray, Gulf Publishing Company, 1988, the contents of which are hereby incorporated by reference.
[0029] In the following Examples, the following commercial products available from Baker Hughes INTEQ were used: CARBOGEL, a quaternized clay; OMNI-MUL, a polyamide emulsifier; CLAYTROL, a water soluble shale hydration and dispersion inhibitor for water based drilling fluids; DFE-434, a quaternized clay; MIL-BARTM a barite additive; MIL-GELTM, a ground montmorillonite used to simulate formation shale contaminant. The following commercial products, available from sources other than Baker Hughes INTEQ were used: CF-2002, an ester/olefin blend available from Chevron Phillips Chemical Co.; C16, C18 isomerized olefins obtained from Chevron Phillips Chemical Co.; LUBRIZOL (R) 3702 and LUBRIZOL (R) 7720C, rheological modifiers available from the Lubrizol Corporation; REV-DUSTTM, a simulated drilled product which may be obtained from Mil-White Company, Houston, Texas; RHODIA
CS-50, a formate salt of 1,6-diamine hexane, and RHODIA CS-60, a chloride salt of 1,6,-diamine hexane. The following organofunctional compounds are available from a variety of commercial sources: aminoethylpiperazine; diaminocyclohexane;
hexamethylenetriamine; urea; triethanolamine; aminoethylethanolamine;
hexamethylenediamine; 2-amino-2-methyl-1-propanol; and, tetraethylenepentamine.
[0030] The invention will be better understood with reference to the examples which are illustrative only:
Example I
[0031] In order to determine the desired composition of a suitable base fluid, a variety of invert emulsion fluids were made using CF-2002 as the continuous phase and MIL-GEL NT as the contaminant. The invert emulsion fluids were subjected to standard testing to determine rheological and fluid loss properties. The compositions tested and the results are given in the following Table:
OP-499:
12.0 lb/gal CF-2002, using Seawater as Brine Phase Sample No. 1 1-S2 2-S 3 3-S4 4-S5 5-S6 6-S
CF-2002, 0.5750.5750.5750.5750.5750.5750.5750.5750.5750.5750.5750.575 bbl CARBOGEL, 2 2 2 2 Ib OMNI-MUL, 14 14 14,14 14 14 14 14 14 14 14 14 lb Seawater, 0.2 0.20.1710.1710.20.20.1710.1710.1710.1710.1710.171 bbl CLAY-TROL, 10 10 10 10 10 10 10 10 lb Lubrizol 3 3 (R) 3702, lb Lubrizol 3 3 (R) 7720C, lb S, lb MILBAR,Ib 255 255255255 255255255 255255 255255255 MIL-GEL 54* 54* 27 27 27 27 NT, lb O/W Ratio 80/2080/2080/2080/2080/2080/2080/2080/2080/2080/2080/2080/20 Density, 12 12 12 12 12 12 12 12 12 12 12 12 lb/gal Samples hot-rolled 16 hours @
150F. Stirred minutes.
Plastic 17 33 20 41 18 34 18 30 19 28 20 30 Viscosity, Cp ~,a7 120F
Yield Point,13 18 17 28 6 22 8 7 12 19 11 13 Ib/100 sq ft 10-sec Gel,5 8 8 14 3 10 4 6 5 8 5 7 lb/100 sq ft 10-min Gel,1b11006 10 9 16 3 14 4 8 6 9 5 9 sq ft Electrical 400 260700480 170305270 400350 365330340 stability, volts HTHP, 30 11 16 18 16 20 20 min @
250F, ml Water in 0.5 0.5 0.5 1 1 1 filtrate, ml * Rev-Dust used As seen from the foregoing, fluid loss was observed in the samples to which contaminant was added.
Example II
[0032] Again, variety of invert emulsion fluids were made using either CF-2002 or C-16,18 olefin as the continuous phase and using the compositions given in the following Table. The fluids were subjected to standard testing to determine Theological and fluid loss properties. The results are given in the following Table:
OP-499:
12.0 lb/gal or C-16,18, using Seawater as Brine Phase Sample No. 7 7-S8 8-S 9 9-S 10 10-S11 11-S12 12-S
CF-2002, 0.5750.5750.5750.5750.5750.575 bbl C-16, 18, 0.5750.5750.5750.5750.5750.575 bbl OMNI-MUL, 14 14 14 14 20 20 20 20 lb E, lb Seawater, 0.1710.1710.1710.1710.1710.1710.1710.1710.1710.1710.1710.171 bbl CARBOGEL, 1 1 1 1 1 1 1 1 1 1 lb SD-1, lb 1 1 CLAY-TROL, 10 10 10 10 10 10 10 10 10 10 lb Rhodia CS-60, 10 10 Ib Lubrizol 3 3 3 3 3 3 3 3 3 3 3 3 (R) 7720C, lb S, lb MILBAR,Ib 255 255255255 255255 255255255 255255255 NT, lb O/W Ratio 80/2080/2080/2080/2080/2080/2080/208012080/2080/2080/2080/20 Density, 12 12 12 12 12 12 12 12 12 12 12 12 lb/gal Samples hot-rolled 16 hours @
150F. Stirred minutes.
Plastic 19 31 19 29 20 35 17 30 18 30 18 23 Viscosity, Cp Yield Point,8 21 5 9 5 18 10 17 9 20 5 9 lb/100 sq ft 10-sec Gel,5 10 4 7 4 9 5 12 4 11 4 6 lb/100 sq ft 10-min Gel,6 13 5 9 5 12 6 14 5 13 5 8 Ib/100 sq ft Electrical 300 475300425 400550 550680210 550230510 stability, volts HTHP, 30 10 18 6 8 14 22 min @
Water in 0.5 1 0.5 0.5 1 1 filtrate, ml Again, fluid loss was observed in the samples to which contaminant was added.
Examule III
[0033] C-16, 18 invert emulsions were tested with and without contaminant and with and without BIOCOTE, a polyamide wetting agent, available from Baker Hughes INTEQ, in order to determine whether the wetting agent would successfully prevent fluid loss. The following were the results:
OP-499:Ib/gal 02 or 12.0 CF-20 C-16,18,ing Seawateras us Bri ne Phase Sample 13 13-S 14 14-S 15-S16-S 17-S18 18-S 19 19-S
No. 14- 17 ST
CF-2002, bbl C-16, 0.575 0.575 0.5750.5750.575 0.5750.575 0.5750.575 18, 0.575 0.575 0.575 0.575 bbl OMNI-MUL,10 10 20 20 20 14 14 14 14 14 14 14 14 lb OMNI-TEC,4 4 lb Lime, 3 3 lb Seawater,0.171 0.171 0.1710.1710.171 0.20.2 0.2 0.1860.186 bbl 0.171 0.171 0.2 CARBOGEL,1 1 lb DFE-434, 1 1 1 1 1 1 1 1 1 1 1 lb ____........_........._..............._.........._..._........-._............_......__~.__._....._._..__...._...__.___....____........_.......
.._......__.............._ CLAY- _.._.._........_.__........_10 ............___..._ _.........._....._5 5 10 10 _....__~...... 10 TROL, lb Lubrizol3 3 3 3 3 3 3 3 3 3 3 3 (R) 3 7720C, ~
lb S, lb MILBAR,Ib255 255 255 255 255 255 255255 255 255255 NT, lb Ratio 80/20 80/20 80/20 80/20 Density,12 12 12 12 12 12 12 12 12 12 12 12 12 lb/gal ........._.._p..__.._._._..._..._.....__........_._ _....__..._.__~
_....__.__.__....._.._...._........__ _.._.__.___.lled ~. ...........__...... __..
_....__......._..._._.__.. _.._.__..._ _.. 16 ...........__._.__.. _.._.._....__.
Sam les hot ro hours . Stirred @ 150F 5 minutes.
Plastic19 21 18 26 27 22 24 18 29 17 29 20 28 Viscosity, Cp a Yield 1 5 18 31 18 16 14 10 26 19 27 10 17 Point, lb/100 sq ft 10-sec 2 5 7 15 6 6 5 4 7 7 12 5 7 Gel, lb/100 sq ft 10-min 3 9 8 16 7 7 7 5 9 8 16 5 8 Gel, lb/100 sq ft Electrical280 340 400 650 380 400 340300 410 280420 stability, volts HTHP, >50 7 4 15 4 7 5 4 min @ 250F
Water in 2 0.5 filtrate, ml OP-499:
12.0 lb/gal or C-16,18, using Seawater as Brine Phase _.._ Sample 20 20-S
No.
::F-2002, _ bbl -16, 0.575 18, 0.575 bbl ~MNI-MUL,14 14 b CMNI-TEC, ~b Lime, _ __ lb Seawater,0.186 bbl 0.186 _....
CARBOGEL, Ib DFE-434,1 1 lb TROL, _..__..._......_.__...____...
............._..:....._..._._._.._..__.....___. ....___.._,..
lb...__............_.......__.... .-.. _._.. ..____... ......_.._.~.
-..........~.. _..................._..
.............._......_.
Lubrizol (R) 7720C, lb S, Ib MILBAR,255 lb 255 NT, lb Ratio 80/20 80/20 80/20 80/20 80/20 Density,12 12 12 12 12 12 12 12 12 12 12 12 12 lb/gal Samplesolled hot-r 16 hours F. Stirred @ 150 5 minutes.
Plastic18 26 Viscosity, Cp @ 120F _ Yield 10 13 Point, _lb/100 sq ft 10-sec 4 6 Gel, 1b1100 sq ft 10-min 4 7 Gel, 'lb/100 _ sq ft 'Electrical400 ~ stability, volts HTHP, ~ 11 min Water in filtrate, ml The use of the wetting agent BIO-COTETM prevented the contaminated samples from exhibiting fluid loss.
Example IV
[0034] Having determined a preferred base fluid, a variety of organofunctional amines were added to the base fluid and the shale inhibition and rheological properties were compared. A fluid using calcium chloride as the non-oleaginous phase was also tested for comparison. All of the organoamines were in the form of acetate salts, except for CS-6 (formate salt) and CS-60 (chloride salt). The following parameters (after hot rolling) were used to select candidates with effective rheology and fluid loss control properties:
Plastic Viscosity (PV), Cp 26-30 @ 120 F
Yield Point (YP), lb/100 sq 12-18 ft 10-sec Gel, lb/100 sq ft 4-8 10-min Gel, lb/100 sq ft 5-10 Electrical stability, volts 350-450 HTHP, 30 min @ 250 F 6 or less Water in filtrate, ml none Organofunctional compounds that exhibited electrical stability of 350-450 volts and HTHP (high temperature high pressure differential filtration) of 6 or less are defined as "effective to provide shale inhibition" in the invert emulsion fluid.
[0035] The results are given in Fig. 1. The candidate containing tetraethylenepentamine was the only candidate containing BIOCOTE which exhibited fluid loss with detrimental water phase. Based on the results in Fig. I, the following candidates were identified as exhibiting effective rheology and fluid loss control properties:
CLAYTROL
Diaminocyclohexane Triethanolamine Hexamethylenediamine Although the plastic viscosity and yield point were not ideal, urea also was identified as a preferred candidate because of its wide availability and relative lack of toxicity.
Example V
[0036] Shale inhibition and rheological properties were compared for base fluids containing seawater vs. 25% calcium chloride as the non-oleaginous phase. The following parameters (after hot rolling) were measured:
Sample No. 37-S 38-S 39-S 40-S 41-S 42-S
C-16, 18, bbl 0.576 0.5830.5400.5440.575 0.575 OMNI-MUL, Ib 16 16 18 18 14 14 Seawater, bbl 0.11 0.066 0.186 0.186 25% Calcium chloride, 0.111 0.066 bbl Freshwater, bbl DFE-434, Ib 1 1 1 1 1 1 CLAY-TROL, Ib 5 5 Special CLAY-TROL No.
1, Ib Special CLAY-TROL No.
2, Ib CS-50 (1,6-diaminehexane), Ib CS-60 (1,6-diaminehexane), Ib 50% Pure triethanolamine, 5 Ib 50% Pure monoethanolamine, 5 Ib.
Lubrizol (R) 7720C, 3 3 3 3 3 3 Ib CARBO-TEC S, Ib 1 1 1 1 1 1 MILBAR, Ib 342 331 452 445 255 255 BIO-COTE, Ib 2 2 2 2 2 2 MIL-GEL NT, Ib 27 27 27 27 27 27 O/W Ratio 85/15 85/1590/1090/1080/20 Density, Ib/gal 14 14 16 16 12 12 Plastic Viscosity, 30 32 37 46 30 18 Cp @ 120F
Yield Point, Ib/100 5 12 6 14 13 4 sq ft 10-sec Gel, Ib/100 4 4 4 7 5 2 sq ft 10-min Gel, Ib/100 5 5 6 12 7 2 sq ft Electrical stability, 510 650 700 1300 550 170 volts HTHP, 30 min @ 250F 8 10 7 9 6 26 Water in filtrate, ml The samples formulated with seawater demonstrated improved stability compared to the calcium chloride samples.
Example VI
[0037] A study was performed to compare CLAYTROL with triethanolamine. The following were the results:
Sample No. 43-S 44-S 45-S 46-S
C-16, 18, bbl 0.575 0.5750.575 0.575 OMNI-MUL, Ib OMNI-MUL (Witco 350783),14 14 14 14 Ib Seawater, bbl 0.186 0.1860.186 0.186 DFE-434, Ib 1 1 1 1 Lubrizol (R) 7720C, 3 3 3 3 Ib CLAY-TROL, Ib 5 5 Triethanolamine, Ib 5 5 CARBO-TEC S, Ib 1 1 1 1 MILBAR, Ib 255 255 255 255 BIO-COTE, Ib 2 2 MIL-GEL NT, Ib 27 27 27 27 O/W Ratio 80/20 80/2080/20 80/20 Density, Ib/gal 12 12 12 12 Plastic Viscosity, 25 27 25 31 Cp @ 120F
Yield Point, Ib/100 40 20 24 21 sq ft 10-sec Gel, Ib/100 17 7 13 8 sq ft 10-min Gel, Ib/100 18 8 15 10 sq ft Electrical stability, 320 240 420 550 volts HTHP, 30 min @ 250F 32 8 17 6 Water in filtrate, 8 1 2 1 ml [0038] Persons of ordinary skill in the art will recognize that many modifications may be made to the present invention without departing from the spirit and scope of the present invention. The embodiment described herein is meant to be illustrative only and should not be taken as limiting the invention, which is defined in the following claims.
20' [0017] The exchangeable groups preferably are derived from primary functional groups. Most preferably, the organofunctional compound comprises at least two primary functional groups. By "primary functional groups" is meant a functional group which is bound to a single alkyl moiety. For example, an alkyl amine is a primary functional group. A dialkyl amine is not a primary functional group.
[0018] Examples of primary functional groups comprising suitable exchangeable groups include, but are not necessarily limited to nitrogen containing groups, oxygen containing groups, sulfur containing groups, and phosphorus containing groups.
Preferred primary functional groups are selected from the group consisting of amine groups, hydroxyl groups, and salts thereof. More preferred primary functional groups are selected from the group consisting of amine groups and salts thereof, preferably amine groups and protonated amine groups. Even more preferably, the organofunctional compound is selected from the group consisting of a diamine and salts thereof, most preferably an alkylenediamine wherein the alkyl moiety comprises from about 1 to about 7 to carbon atoms, preferably from about 2 to about 7 carbon atoms, and more preferably from about 2 to about 6 carbon atoms, wherein the carbon atoms may be joined to form a cycloalkyl.
[0019] Suitable organofunctional compounds for use in the dispersed phase have the following general structure:
x R Y
wherein X and Y independently are primary functional groups comprising exchangeable groups. Preferably, X and Y independently are selected from the group consisting of nitrogen containing groups, oxygen containing groups, sulfur containing groups, and phosphorus containing groups. More preferably X and Y independently are selected from the group consisting of amine groups, hydroxyl groups, and salts thereof; most preferably both X and Y
independently are selected from the group consisting of amine groups and salts thereof;
R is selected from the group consisting of linear alkylene groups having from about 1 to about 7 carbon atoms, preferably from about 2 to about 7 carbon atoms, most preferably from about 2 to about 6 carbon atoms, and cyclic alkylene groups having from about 3 to about 6 carbon atoms, wherein R is either unsubstituted or bears substituents effective to maintain or increase the dissociability of the exchangeable groups. For example, where the exchangeable group is cationic in nature, acceptable substituents either would not affect the charge distribution of the molecule or would be electrophilic or cationic in nature.
[0020] In a preferred embodiment, the organofunctional salt is selected from the group consisting of urea, alkanolamines, diaminocycloalkanes, substituted or unsubstituted alkylene diaminesand, combinations thereof. In a more preferred embodiment, the organic material is selected from the group consisting of substituted or unsubstituted trialkanolamines; diaminocycloalkanes; alkylene diamines;
and, combinations thereof. In a most preferred embodiment, the organofunctional compounds are selected from the group consisting of substituted or unsubstituted triethanolamines, diaminocyclohexanes, hexarnethylenediamines, salts thereof, and combinations thereof. A preferred commercially available mixture is CLAYTROLTM, which is commercially available from Baker Hughes INTEQ.
[0021] A given organofunctional compound is "effective to provide shale inhibition"
when the organofunctional compound produces an invert emulsion fluid that exhibits electrical stability of 350-450 volts and HTHP (high temperature high pressure differential filtration) of 6 or less.
[0022] The amount of non-oleaginous liquid in the invert emulsion fluid varies depending upon the particular non-oleaginous liquid used and the particular application in which the invert emulsion fluid is to be employed. The amount of non-. oleaginous liquid is effective to produce a stable emulsion and decreases with the density of the fluid. Typically, the amount of non-oleaginous liquid is at least about 1 vol.%, preferably from about 1 vol.% to about 50 vol.% or less of the total invert emulsion fluid.
[0023] The invert emulsions generally may comprise other components known in the art. Composition and Properties of Drilling and Completion Fluids, 5th Edition, H. C.
H. Darley, George R. Gray, Gulf Publishing Company, 1988, pp. 328-332, incorporated by reference. Conventional additives include, but are not necessarily limited to shale stabilizers) other than the organofunctional compound(s), filtration control additive(s), 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-linker(s), catalyst(s), soluble salts, biocides, and combinations thereof. Lime or another alkaline material may be added to an invert emulsion fluid to maintain a reserve alkalinity and to counter acidic gases, which often are encountered during drilling operations.
[0024] In a preferred embodiment, the invert emulsion fluid comprises:
emulsifier(s), clay(s), preferably quaternized clay(s), rheological modifier(s), preferably acrylate or methacrylate based modifier(s), weighting agent(s), and, wetting agents) effective to prevent fluid loss. A preferred type of wetting agent is a polyolefin amide alkene amine wetting agent, most preferably BIO-COTETM, available from Baker Hughes INTEQ.
[0025] Substantially any method may be used to prepare the invert emulsion drilling system fluids of the present invention as long as the method is effective to form an invert emulsion. Generally, the components are mixed together in any order under agitation conditions. In a preferred embodiment, an appropriate quantity of non-oleaginous liquid is mixed with an appropriate quantity of the organofunctional compound and, if necessary or desired, an acid to protonate the organofunctional compound. The resulting mixture is subjected to mild agitation. An oleaginous fluid is then added while mixing until an invert emulsion is formed. If a weight material is to be used, then the weight material typically is added after the invert emulsion fluid is formed.
[0026] One skilled in the art may readily identify whether the~appropriate ingredients and amounts have been used to form the invert emulsion using the following test:
Invert Emulsion Test [0027] A small portion of the emulsion is placed in a beaker which contains an oleaginous fluid. If the emulsion is an invert emulsion, the small portion will disperse in the oleaginous fluid. Visual inspection determines whether the small portion added has dispersed.
[0028] Alternately, the electrical stability of the invert emulsion is tested using known procedures. Generally, voltage is applied across two electrodes immersed in the emulsion, and the voltage is increased until the emulsion breaks and a surge of current flows between the two electrodes. The voltage required to break the emulsion is a common measure of the stability of an emulsion. Other tests are described on page 166 of the book, Composition and Properties of Drilling and Completion Fluids, 5th Edition, H. C. H. Darley and George Gray, Gulf Publishing Company, 1988, the contents of which are hereby incorporated by reference.
[0029] In the following Examples, the following commercial products available from Baker Hughes INTEQ were used: CARBOGEL, a quaternized clay; OMNI-MUL, a polyamide emulsifier; CLAYTROL, a water soluble shale hydration and dispersion inhibitor for water based drilling fluids; DFE-434, a quaternized clay; MIL-BARTM a barite additive; MIL-GELTM, a ground montmorillonite used to simulate formation shale contaminant. The following commercial products, available from sources other than Baker Hughes INTEQ were used: CF-2002, an ester/olefin blend available from Chevron Phillips Chemical Co.; C16, C18 isomerized olefins obtained from Chevron Phillips Chemical Co.; LUBRIZOL (R) 3702 and LUBRIZOL (R) 7720C, rheological modifiers available from the Lubrizol Corporation; REV-DUSTTM, a simulated drilled product which may be obtained from Mil-White Company, Houston, Texas; RHODIA
CS-50, a formate salt of 1,6-diamine hexane, and RHODIA CS-60, a chloride salt of 1,6,-diamine hexane. The following organofunctional compounds are available from a variety of commercial sources: aminoethylpiperazine; diaminocyclohexane;
hexamethylenetriamine; urea; triethanolamine; aminoethylethanolamine;
hexamethylenediamine; 2-amino-2-methyl-1-propanol; and, tetraethylenepentamine.
[0030] The invention will be better understood with reference to the examples which are illustrative only:
Example I
[0031] In order to determine the desired composition of a suitable base fluid, a variety of invert emulsion fluids were made using CF-2002 as the continuous phase and MIL-GEL NT as the contaminant. The invert emulsion fluids were subjected to standard testing to determine rheological and fluid loss properties. The compositions tested and the results are given in the following Table:
OP-499:
12.0 lb/gal CF-2002, using Seawater as Brine Phase Sample No. 1 1-S2 2-S 3 3-S4 4-S5 5-S6 6-S
CF-2002, 0.5750.5750.5750.5750.5750.5750.5750.5750.5750.5750.5750.575 bbl CARBOGEL, 2 2 2 2 Ib OMNI-MUL, 14 14 14,14 14 14 14 14 14 14 14 14 lb Seawater, 0.2 0.20.1710.1710.20.20.1710.1710.1710.1710.1710.171 bbl CLAY-TROL, 10 10 10 10 10 10 10 10 lb Lubrizol 3 3 (R) 3702, lb Lubrizol 3 3 (R) 7720C, lb S, lb MILBAR,Ib 255 255255255 255255255 255255 255255255 MIL-GEL 54* 54* 27 27 27 27 NT, lb O/W Ratio 80/2080/2080/2080/2080/2080/2080/2080/2080/2080/2080/2080/20 Density, 12 12 12 12 12 12 12 12 12 12 12 12 lb/gal Samples hot-rolled 16 hours @
150F. Stirred minutes.
Plastic 17 33 20 41 18 34 18 30 19 28 20 30 Viscosity, Cp ~,a7 120F
Yield Point,13 18 17 28 6 22 8 7 12 19 11 13 Ib/100 sq ft 10-sec Gel,5 8 8 14 3 10 4 6 5 8 5 7 lb/100 sq ft 10-min Gel,1b11006 10 9 16 3 14 4 8 6 9 5 9 sq ft Electrical 400 260700480 170305270 400350 365330340 stability, volts HTHP, 30 11 16 18 16 20 20 min @
250F, ml Water in 0.5 0.5 0.5 1 1 1 filtrate, ml * Rev-Dust used As seen from the foregoing, fluid loss was observed in the samples to which contaminant was added.
Example II
[0032] Again, variety of invert emulsion fluids were made using either CF-2002 or C-16,18 olefin as the continuous phase and using the compositions given in the following Table. The fluids were subjected to standard testing to determine Theological and fluid loss properties. The results are given in the following Table:
OP-499:
12.0 lb/gal or C-16,18, using Seawater as Brine Phase Sample No. 7 7-S8 8-S 9 9-S 10 10-S11 11-S12 12-S
CF-2002, 0.5750.5750.5750.5750.5750.575 bbl C-16, 18, 0.5750.5750.5750.5750.5750.575 bbl OMNI-MUL, 14 14 14 14 20 20 20 20 lb E, lb Seawater, 0.1710.1710.1710.1710.1710.1710.1710.1710.1710.1710.1710.171 bbl CARBOGEL, 1 1 1 1 1 1 1 1 1 1 lb SD-1, lb 1 1 CLAY-TROL, 10 10 10 10 10 10 10 10 10 10 lb Rhodia CS-60, 10 10 Ib Lubrizol 3 3 3 3 3 3 3 3 3 3 3 3 (R) 7720C, lb S, lb MILBAR,Ib 255 255255255 255255 255255255 255255255 NT, lb O/W Ratio 80/2080/2080/2080/2080/2080/2080/208012080/2080/2080/2080/20 Density, 12 12 12 12 12 12 12 12 12 12 12 12 lb/gal Samples hot-rolled 16 hours @
150F. Stirred minutes.
Plastic 19 31 19 29 20 35 17 30 18 30 18 23 Viscosity, Cp Yield Point,8 21 5 9 5 18 10 17 9 20 5 9 lb/100 sq ft 10-sec Gel,5 10 4 7 4 9 5 12 4 11 4 6 lb/100 sq ft 10-min Gel,6 13 5 9 5 12 6 14 5 13 5 8 Ib/100 sq ft Electrical 300 475300425 400550 550680210 550230510 stability, volts HTHP, 30 10 18 6 8 14 22 min @
Water in 0.5 1 0.5 0.5 1 1 filtrate, ml Again, fluid loss was observed in the samples to which contaminant was added.
Examule III
[0033] C-16, 18 invert emulsions were tested with and without contaminant and with and without BIOCOTE, a polyamide wetting agent, available from Baker Hughes INTEQ, in order to determine whether the wetting agent would successfully prevent fluid loss. The following were the results:
OP-499:Ib/gal 02 or 12.0 CF-20 C-16,18,ing Seawateras us Bri ne Phase Sample 13 13-S 14 14-S 15-S16-S 17-S18 18-S 19 19-S
No. 14- 17 ST
CF-2002, bbl C-16, 0.575 0.575 0.5750.5750.575 0.5750.575 0.5750.575 18, 0.575 0.575 0.575 0.575 bbl OMNI-MUL,10 10 20 20 20 14 14 14 14 14 14 14 14 lb OMNI-TEC,4 4 lb Lime, 3 3 lb Seawater,0.171 0.171 0.1710.1710.171 0.20.2 0.2 0.1860.186 bbl 0.171 0.171 0.2 CARBOGEL,1 1 lb DFE-434, 1 1 1 1 1 1 1 1 1 1 1 lb ____........_........._..............._.........._..._........-._............_......__~.__._....._._..__...._...__.___....____........_.......
.._......__.............._ CLAY- _.._.._........_.__........_10 ............___..._ _.........._....._5 5 10 10 _....__~...... 10 TROL, lb Lubrizol3 3 3 3 3 3 3 3 3 3 3 3 (R) 3 7720C, ~
lb S, lb MILBAR,Ib255 255 255 255 255 255 255255 255 255255 NT, lb Ratio 80/20 80/20 80/20 80/20 Density,12 12 12 12 12 12 12 12 12 12 12 12 12 lb/gal ........._.._p..__.._._._..._..._.....__........_._ _....__..._.__~
_....__.__.__....._.._...._........__ _.._.__.___.lled ~. ...........__...... __..
_....__......._..._._.__.. _.._.__..._ _.. 16 ...........__._.__.. _.._.._....__.
Sam les hot ro hours . Stirred @ 150F 5 minutes.
Plastic19 21 18 26 27 22 24 18 29 17 29 20 28 Viscosity, Cp a Yield 1 5 18 31 18 16 14 10 26 19 27 10 17 Point, lb/100 sq ft 10-sec 2 5 7 15 6 6 5 4 7 7 12 5 7 Gel, lb/100 sq ft 10-min 3 9 8 16 7 7 7 5 9 8 16 5 8 Gel, lb/100 sq ft Electrical280 340 400 650 380 400 340300 410 280420 stability, volts HTHP, >50 7 4 15 4 7 5 4 min @ 250F
Water in 2 0.5 filtrate, ml OP-499:
12.0 lb/gal or C-16,18, using Seawater as Brine Phase _.._ Sample 20 20-S
No.
::F-2002, _ bbl -16, 0.575 18, 0.575 bbl ~MNI-MUL,14 14 b CMNI-TEC, ~b Lime, _ __ lb Seawater,0.186 bbl 0.186 _....
CARBOGEL, Ib DFE-434,1 1 lb TROL, _..__..._......_.__...____...
............._..:....._..._._._.._..__.....___. ....___.._,..
lb...__............_.......__.... .-.. _._.. ..____... ......_.._.~.
-..........~.. _..................._..
.............._......_.
Lubrizol (R) 7720C, lb S, Ib MILBAR,255 lb 255 NT, lb Ratio 80/20 80/20 80/20 80/20 80/20 Density,12 12 12 12 12 12 12 12 12 12 12 12 12 lb/gal Samplesolled hot-r 16 hours F. Stirred @ 150 5 minutes.
Plastic18 26 Viscosity, Cp @ 120F _ Yield 10 13 Point, _lb/100 sq ft 10-sec 4 6 Gel, 1b1100 sq ft 10-min 4 7 Gel, 'lb/100 _ sq ft 'Electrical400 ~ stability, volts HTHP, ~ 11 min Water in filtrate, ml The use of the wetting agent BIO-COTETM prevented the contaminated samples from exhibiting fluid loss.
Example IV
[0034] Having determined a preferred base fluid, a variety of organofunctional amines were added to the base fluid and the shale inhibition and rheological properties were compared. A fluid using calcium chloride as the non-oleaginous phase was also tested for comparison. All of the organoamines were in the form of acetate salts, except for CS-6 (formate salt) and CS-60 (chloride salt). The following parameters (after hot rolling) were used to select candidates with effective rheology and fluid loss control properties:
Plastic Viscosity (PV), Cp 26-30 @ 120 F
Yield Point (YP), lb/100 sq 12-18 ft 10-sec Gel, lb/100 sq ft 4-8 10-min Gel, lb/100 sq ft 5-10 Electrical stability, volts 350-450 HTHP, 30 min @ 250 F 6 or less Water in filtrate, ml none Organofunctional compounds that exhibited electrical stability of 350-450 volts and HTHP (high temperature high pressure differential filtration) of 6 or less are defined as "effective to provide shale inhibition" in the invert emulsion fluid.
[0035] The results are given in Fig. 1. The candidate containing tetraethylenepentamine was the only candidate containing BIOCOTE which exhibited fluid loss with detrimental water phase. Based on the results in Fig. I, the following candidates were identified as exhibiting effective rheology and fluid loss control properties:
CLAYTROL
Diaminocyclohexane Triethanolamine Hexamethylenediamine Although the plastic viscosity and yield point were not ideal, urea also was identified as a preferred candidate because of its wide availability and relative lack of toxicity.
Example V
[0036] Shale inhibition and rheological properties were compared for base fluids containing seawater vs. 25% calcium chloride as the non-oleaginous phase. The following parameters (after hot rolling) were measured:
Sample No. 37-S 38-S 39-S 40-S 41-S 42-S
C-16, 18, bbl 0.576 0.5830.5400.5440.575 0.575 OMNI-MUL, Ib 16 16 18 18 14 14 Seawater, bbl 0.11 0.066 0.186 0.186 25% Calcium chloride, 0.111 0.066 bbl Freshwater, bbl DFE-434, Ib 1 1 1 1 1 1 CLAY-TROL, Ib 5 5 Special CLAY-TROL No.
1, Ib Special CLAY-TROL No.
2, Ib CS-50 (1,6-diaminehexane), Ib CS-60 (1,6-diaminehexane), Ib 50% Pure triethanolamine, 5 Ib 50% Pure monoethanolamine, 5 Ib.
Lubrizol (R) 7720C, 3 3 3 3 3 3 Ib CARBO-TEC S, Ib 1 1 1 1 1 1 MILBAR, Ib 342 331 452 445 255 255 BIO-COTE, Ib 2 2 2 2 2 2 MIL-GEL NT, Ib 27 27 27 27 27 27 O/W Ratio 85/15 85/1590/1090/1080/20 Density, Ib/gal 14 14 16 16 12 12 Plastic Viscosity, 30 32 37 46 30 18 Cp @ 120F
Yield Point, Ib/100 5 12 6 14 13 4 sq ft 10-sec Gel, Ib/100 4 4 4 7 5 2 sq ft 10-min Gel, Ib/100 5 5 6 12 7 2 sq ft Electrical stability, 510 650 700 1300 550 170 volts HTHP, 30 min @ 250F 8 10 7 9 6 26 Water in filtrate, ml The samples formulated with seawater demonstrated improved stability compared to the calcium chloride samples.
Example VI
[0037] A study was performed to compare CLAYTROL with triethanolamine. The following were the results:
Sample No. 43-S 44-S 45-S 46-S
C-16, 18, bbl 0.575 0.5750.575 0.575 OMNI-MUL, Ib OMNI-MUL (Witco 350783),14 14 14 14 Ib Seawater, bbl 0.186 0.1860.186 0.186 DFE-434, Ib 1 1 1 1 Lubrizol (R) 7720C, 3 3 3 3 Ib CLAY-TROL, Ib 5 5 Triethanolamine, Ib 5 5 CARBO-TEC S, Ib 1 1 1 1 MILBAR, Ib 255 255 255 255 BIO-COTE, Ib 2 2 MIL-GEL NT, Ib 27 27 27 27 O/W Ratio 80/20 80/2080/20 80/20 Density, Ib/gal 12 12 12 12 Plastic Viscosity, 25 27 25 31 Cp @ 120F
Yield Point, Ib/100 40 20 24 21 sq ft 10-sec Gel, Ib/100 17 7 13 8 sq ft 10-min Gel, Ib/100 18 8 15 10 sq ft Electrical stability, 320 240 420 550 volts HTHP, 30 min @ 250F 32 8 17 6 Water in filtrate, 8 1 2 1 ml [0038] Persons of ordinary skill in the art will recognize that many modifications may be made to the present invention without departing from the spirit and scope of the present invention. The embodiment described herein is meant to be illustrative only and should not be taken as limiting the invention, which is defined in the following claims.
Claims (30)
1. An invert emulsion drilling system fluid with effective rheology and fluid loss control properties, said drilling system fluid comprising an oleaginous continuous phase and a non-oleaginous dispersed phase, said dispersed phase comprising an amount of at least one organofunctional compound effective to provide shale inhibition.
2. The invert emulsion drilling system fluid of claim 1 selected from the group consisting of a drilling fluid and a drill-in fluid.
3. The invert emulsion drilling system fluid of claim 3 wherein said -oleaginous continuous phase comprises olefins selected from the group consisting of isomerized olefins, linear alpha olefins, and combinations thereof, a majority of said olefins having 16 carbon atoms or more.
4. The invert emulsion drilling system fluid of claim 3 wherein said organofunctional compound has the following general structure:
X~ R ~ Y
wherein X and Y independently are primary functional groups comprising exchangeable groups effective to provide shale inhibition;
R is selected from the group consisting of linear alkylene groups having from about 1 to about 7 carbon atoms and cyclic alkylene groups, wherein R
is either unsubstituted or comprises one or more substituent effective to maintain said exchangeable groups in dissociable form.
X~ R ~ Y
wherein X and Y independently are primary functional groups comprising exchangeable groups effective to provide shale inhibition;
R is selected from the group consisting of linear alkylene groups having from about 1 to about 7 carbon atoms and cyclic alkylene groups, wherein R
is either unsubstituted or comprises one or more substituent effective to maintain said exchangeable groups in dissociable form.
5. The drilling system fluid of claim 3 wherein:
X and Y independently are selected from the group consisting of nitrogen containing groups, oxygen containing groups, sulfur containing groups, and phosphorus containing groups; and, R is selected from the group consisting of linear alkylene groups having from 2 to about 6 carbon atoms and cyclic alkylene groups having from about 3 to about 6 carbon atoms.
X and Y independently are selected from the group consisting of nitrogen containing groups, oxygen containing groups, sulfur containing groups, and phosphorus containing groups; and, R is selected from the group consisting of linear alkylene groups having from 2 to about 6 carbon atoms and cyclic alkylene groups having from about 3 to about 6 carbon atoms.
6. The drilling system fluid of claim 3 wherein:
X and Y independently are selected from the group consisting of amine groups, hydroxyl groups, and salts thereof; and, R is selected from the group consisting of linear alkylene groups having from 2 to about 6 carbon atoms and cyclic alkylene groups having from about 3 to about 6 carbon atoms.
X and Y independently are selected from the group consisting of amine groups, hydroxyl groups, and salts thereof; and, R is selected from the group consisting of linear alkylene groups having from 2 to about 6 carbon atoms and cyclic alkylene groups having from about 3 to about 6 carbon atoms.
7. The invert emulsion drilling system fluid of claim 3 wherein said organofunctional compound comprising an active ingredient selected from the group consisting of triethanolamine, alkylenediamine, alkylenediamine salts, and combinations thereof.
8. The invert emulsion drilling system fluid of claim 7 wherein said organofunctional compound comprises an alkylene group having from about 1 to about 7 carbon atoms, wherein the carbon atoms comprise an entity selected from the group consisting of a linear entity, a branched entity, and a cycloalkyl entity.
9. The invert emulsion drilling system fluid of claim 8 wherein a majority of said olefins have from about 16 to about 18 carbon atoms.
10. The invert emulsion drilling system fluid of claim 9 further comprising comprising a quantity of a polyolefin amide alkene amine.
11. The invert emulsion drilling system fluid of any of claims 1-9 and 10 wherein said organofunctional compound comprises an active ingredient selected from the group consisting of diaminocyclohexane, salts of diaminocyclohexane, and combinations thereof.
12. The invert emulsion drilling system fluid of claim 11 further comprising comprising a quantity of a polyolefin amide alkene amine.
13. The invert emulsion of any of claims 1-30 and 31 wherein said organofunctional compound comprises hexamethylenediamine.
14. The invert emulsion drilling system fluid of claim 13 further comprising comprising a quantity of a polyolefin amide alkene amine.
15. The invert emulsion of any of claims 1-30 and 31 wherein said organofuncitonal compound comprises CLAYTROL.TM..
16. The invert emulsion drilling system fluid of any of claims 1-30 and 31 wherein said organofunctional compound comprises an active ingredient selected from the groupconsisting of urea, salts of urea, and combinations thereof.
17. The invert emulsion drilling system fluid of claim 3 wherein said organofunctional compound comprises a quantity and type of exchangeable groups effective to provide shale inhibition.
18. The invert emulsion drilling system fluid of claim 17 wherein said organofunctional compound comprises a quantity of primary functional groups effective to provide said quantity and type of exchangeable groups.
19. The invert emulsion drilling system fluid of claim 18 wherein said exchangeable groups are cations.
20. The invert emulsion drilling system fluid of claim 19 wherein said primary functional groups are selected from the group consisting of nitrogen containing groups, oxygen containing groups, sulfur containing groups, and phosphorus containing groups.
21. The invert emulsion drilling system fluid of claim 20 wherein said primary functional groups are selected from the group consisting of amine groups, hydroxyl groups, and salts thereof.
22. The invert emulsion drilling system fluid of any of claims 17-20 and 21 wherein said at least one organofunctional compound comprises at least two primary functional groups comprising a quantity and type of exchangeable groups effective to provide shale inhibition.
23. The invert emulsion drilling system fluid of any of claims 17-20 and 21 further comprising comprising a quantity of a polyolefin amide alkene amine.
24. The invert emulsion drilling system fluid of claim 22 further comprising comprising a quantity of a polyolefin amide alkene amine.
25. A method for reducing the concentration of inorganic salts required to provide shale inhibition during drilling operations using invert emulsion drilling system fluids comprising an oleaginous continuous phase and a non-oleaginous dispersed phase, said method comprising providing said non-oleaginous dispersed phase of said fluid with an amount of an organofunctional compound effective to provide shale inhibition.
26. The method of claim 25 wherein said cationic exchangeable groups are derived from primary functional groups selected from the group consisting of nitrogen containing groups, oxygen containing groups, sulfur containing groups, and phosphorus containing groups.
27. The method of claim 26 wherein said cationic exchangeable groups are derived from primary functional groups selected from the group consisting of amine groups, hydroxyl groups, and salts thereof.
28. The method of claim 27 wherein said organofunctional compound comprises at least two primary functional groups comprising said cationic exchangeable groups.
29. The method of claim 28 wherein said organofunctional compound has the following general structure:
X~R~Y
wherein X and Y independently are primary functional groups comprising exchangeable groups effective to provide shale inhibition;
R is selected from the group consisting of linear alkylene groups having from about 1 to about 7 carbon atoms and cyclic alkylene groups having from about 3 to about 6 carbon atoms, wherein R is either unsubstituted or comprises one or more substituent effective to maintain said exchangeable groups in dissociable form.
X~R~Y
wherein X and Y independently are primary functional groups comprising exchangeable groups effective to provide shale inhibition;
R is selected from the group consisting of linear alkylene groups having from about 1 to about 7 carbon atoms and cyclic alkylene groups having from about 3 to about 6 carbon atoms, wherein R is either unsubstituted or comprises one or more substituent effective to maintain said exchangeable groups in dissociable form.
30. The method of claim 29 further comprising providing said invert emulsion drilling system fluid with a quantity of a polyolefin amide alkene amine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/294,533 US7067460B2 (en) | 2002-11-14 | 2002-11-14 | Organofunctional compounds for shale stabilization of the aqueous dispersed phase of non-aqueous based invert emulsion drilling system fluids |
| US10/294,533 | 2002-11-14 | ||
| PCT/US2003/036417 WO2004046273A2 (en) | 2002-11-14 | 2003-11-13 | Organofunctional compounds for shale stabilization of the aqueous dispersed phase of non-aqueous based invert emulsion drilling system fluids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2505045A1 CA2505045A1 (en) | 2004-06-03 |
| CA2505045C true CA2505045C (en) | 2011-01-11 |
Family
ID=32296995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2505045A Expired - Fee Related CA2505045C (en) | 2002-11-14 | 2003-11-13 | Organofunctional compounds for shale stabilization of the aqueous dispersed phase of non-aqueous based invert emulsion drilling system fluids |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US7067460B2 (en) |
| AU (1) | AU2003290898B2 (en) |
| CA (1) | CA2505045C (en) |
| GB (1) | GB2410522B (en) |
| NO (1) | NO20052720L (en) |
| WO (1) | WO2004046273A2 (en) |
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| US7749945B2 (en) * | 2000-06-13 | 2010-07-06 | Baker Hughes Incorporated | Invert emulsion drilling fluid systems comprising an emulsified aqueous phase comprising dispersed integral latex particles |
| US20100222241A1 (en) * | 2004-08-06 | 2010-09-02 | Lamberti Spa | Clay Inhibitors for the Drilling Industry |
| CN101014681B (en) * | 2004-08-06 | 2011-04-06 | 蓝宝迪有限公司 | Clay inhibitor for the drilling industry |
| US7803743B2 (en) | 2005-06-06 | 2010-09-28 | Baker Hughes Incorporated | Invert emulsion carrier fluid and oil-wetting agent and method of using same |
| US7740071B2 (en) * | 2005-06-24 | 2010-06-22 | Innovative Chemical Technologies Canada Ltd. | Clay control additive for wellbore fluids |
| US8936111B2 (en) | 2010-03-06 | 2015-01-20 | Halliburton Energy Services, Inc. | Invert drilling fluids having enhanced rheology and methods of drilling boreholes |
| US8950492B2 (en) * | 2011-07-20 | 2015-02-10 | Halliburton Energy Services, Inc. | Invert emulsion fluid containing a hygroscopic liquid, a polymeric suspending agent, and low-density solids |
| US9376608B2 (en) * | 2011-07-20 | 2016-06-28 | Halliburton Energy Services, Inc. | Invert emulsion drilling fluid containing a hygroscopic liquid and a polymeric suspending agent |
| CA2862135A1 (en) * | 2012-01-02 | 2013-07-18 | Halliburton Energy Services, Inc. | Invert drilling fluids having enhanced rheology and methods of drilling boreholes |
| MX2015015807A (en) * | 2013-05-14 | 2017-05-01 | Ingevity South Carolina Llc | Clay inhibitors for drilling, fracturing, and other procedures. |
| WO2015041669A1 (en) | 2013-09-20 | 2015-03-26 | Halliburton Energy Services, Inc. | Methods for enhancing and maintaining fracture conductivity after fracturing shale formations without proppant placement |
| CA3043973A1 (en) | 2016-11-30 | 2018-06-07 | Saudi Arabian Oil Company | Invert emulsion drilling fluids with fatty acid and fatty diol rheology modifiers |
| CN110225956A (en) | 2017-02-03 | 2019-09-10 | 沙特阿拉伯石油公司 | Oil based fluids composition for hydrocarbon exploitation application |
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-
2002
- 2002-11-14 US US10/294,533 patent/US7067460B2/en not_active Expired - Fee Related
-
2003
- 2003-11-13 GB GB0509775A patent/GB2410522B/en not_active Expired - Fee Related
- 2003-11-13 AU AU2003290898A patent/AU2003290898B2/en not_active Ceased
- 2003-11-13 WO PCT/US2003/036417 patent/WO2004046273A2/en not_active Application Discontinuation
- 2003-11-13 CA CA2505045A patent/CA2505045C/en not_active Expired - Fee Related
-
2005
- 2005-06-07 NO NO20052720A patent/NO20052720L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003290898A1 (en) | 2004-06-15 |
| GB2410522B (en) | 2006-07-05 |
| GB0509775D0 (en) | 2005-06-22 |
| NO20052720L (en) | 2005-06-07 |
| US7067460B2 (en) | 2006-06-27 |
| CA2505045A1 (en) | 2004-06-03 |
| AU2003290898B2 (en) | 2011-07-21 |
| WO2004046273A2 (en) | 2004-06-03 |
| GB2410522A (en) | 2005-08-03 |
| WO2004046273A3 (en) | 2004-09-30 |
| US20040097380A1 (en) | 2004-05-20 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20191113 |