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WO1999009109A1 - Additifs stabilisateurs de schiste argileux - Google Patents

Additifs stabilisateurs de schiste argileux Download PDF

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Publication number
WO1999009109A1
WO1999009109A1 PCT/GB1998/002377 GB9802377W WO9909109A1 WO 1999009109 A1 WO1999009109 A1 WO 1999009109A1 GB 9802377 W GB9802377 W GB 9802377W WO 9909109 A1 WO9909109 A1 WO 9909109A1
Authority
WO
WIPO (PCT)
Prior art keywords
drilling fluid
shale
additive
drilling
fluid
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/GB1998/002377
Other languages
English (en)
Inventor
Bernadette Teresa Craster
Terence George Balson
Paul Ian Reid
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sofitech NV
Schlumberger Canada Ltd
Compagnie des Services Dowell Schlumberger SA
Dow Chemical Co
Original Assignee
Sofitech NV
Schlumberger Canada Ltd
Compagnie des Services Dowell Schlumberger SA
Dow Chemical Co
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 Sofitech NV, Schlumberger Canada Ltd, Compagnie des Services Dowell Schlumberger SA, Dow Chemical Co filed Critical Sofitech NV
Priority to BR9814943-1A priority Critical patent/BR9814943A/pt
Priority to AU87366/98A priority patent/AU8736698A/en
Priority to CA002300110A priority patent/CA2300110A1/fr
Publication of WO1999009109A1 publication Critical patent/WO1999009109A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/14—Clay-containing compositions
    • C09K8/18—Clay-containing compositions characterised by the organic compounds
    • C09K8/22—Synthetic organic compounds
    • 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
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/06—Clay-free compositions
    • C09K8/12—Clay-free compositions containing synthetic organic macromolecular compounds or their precursors

Definitions

  • This invention concerns drilling fluids, particularly water- based drilling fluids. More specifically, it pertains to additives for drilling fluids. Even more specifically, the invention relates to additives used to prevent shales from adversely affecting drilling operations.
  • Drilling fluids are used in well drilling operations, e.g., during drilling of oil and gas wells.
  • drilling fluid is pumped down a drillstring, discharged through ports in the drill bit and returned to the surface via the annulus between the drillpipe and the surrounding formation.
  • the drilling fluid performs a variety of functions including cooling and lubricating the drill bit and drillstring, removing rock cuttings generated during the drilling process and carrying them to the surface, suspending cuttings in the annulus when pumping stops, preventing squeezing in or caving of the formation and keeping formation fluids at bay.
  • Drilling fluids generally comprise a carrier, a weighting agent and chemical additives. Drilling fluids fall into two main categories: water-based drilling fluids, also known as water based muds (WBM) , in which the carrier is an aqueous medium; and oil-based drilling fluids, also known as oil-based muds (OBM) , in which the carrier is oil.
  • WBM water based muds
  • OBM oil-based drilling fluids
  • OBM oil-based drilling fluids
  • OBM oil-based drilling fluids
  • OBM are technically superior to WBM in certain important respects, including the comparative lack of adverse reactivity of OBM with shales, one of the most commonly encountered rock types during drilling for oil and gas.
  • Use of OBM however, has the disadvantage of resulting in production of large quantities of oil-contaminated waste products such as cuttings that are difficult to dispose of in an environmentally acceptable way.
  • WBM While use of WBM is environmentally more acceptable than OBM, the performance of WBM, particularly when drilling through water sensitive rocks such as shales, is technically inferior to thac of OBM. Shales exhibit great affinity for water, and adsorption of water by shales causes the shale to swell and produces chemical changes in the rock which produce stresses that weaken the formation, possibly leading to erosion of the borehole or loss of structure. This can lead to drilling problems such as stuck pipe. In addition inferior wellbore quality may hinder logging and completion operations.
  • Polyols used in this way include, for example, glycerols, polyglycerols , glycols, polyalkylene glycols (PAG), eg polyethylene glycols (PEG), polypropylene glycols (PPG) and copolymers of ethylene and propylene glycols, alcohol ethoxylates (AET) and glycol ethers.
  • a typical inhibitive AET is an n-butanol derivative of ethylene oxide.
  • the PAGs can have a range of ethylene oxide: propylene oxide (EO:PO) ratios and can be random or block copolymers; a frequently used material of this type is understood to be a random copoiymer with an EO:PO ratio of about 1:1.
  • reaction products of trihydroxy alkyl amine with an alkyl halide leading to quaternary alkyl amines as additive for shale swelling inhibitors are described in the United States Patent 5,350,740.
  • an aqueous well-drilling fluid comprising at least one non-Newtonian colloidal disperse system , a clay/water slurry, and an emulsifier effective for emulsifying the disperse system in the clay/water slurry.
  • emulsifiers described as being useful are ethoxylated amines and diamine wherein the amine or diamine has at least 12 carbon atoms.
  • a drilling fluid comprising a stable oil in water emulsion consisting of water, oil, and at least one surfactant belonging to the class of alkyl amine ethoxylates wherein the ethoxylates are bond to the nitrogen via an ether (oxygen) bridge.
  • the drilling fluid is described as preventing shale swelling by coating the oil out onto the mineral surfaces.
  • a surfactant for use in a biological assay system.
  • the surfactant is obtained when ethylene diamine is reacted sequentially with propylene oxide and ethylene oxide in the presence of a catalyst, the polyoxyproylene chains of the surfactant having an average molecular weight of between about 750 and 6750.
  • SPE 28960 Mechanism of Shale Inhibition by Polyols in Water Based Drilling Fluids proposes a credible mechanism that adequately describes how such polyols provide shale inhibition. In summary, this publication teaches that two processes are important :
  • the polyols interact with potassium ions on the surfaces of the fine-grained clay minerals that are present in reactive shales. These potassium ions are hydrated but their low hydration energy means that water is easily removed from the cation and the polyol forms a stable complex. Water is less easily removed from sodium or calcium ions and the resulting cation/polyol complexes are weaker: the authors believe this explains the higher level of inhibition obtained with polyols in the presence of potassium. All the established inhibitive polyols studied by the authors are said to derive the bulk of their activity by this mechanism. Other weakly hydrated cations (eg ammonium or caesium) behave in the same way as potassium.
  • weakly hydrated cations eg ammonium or caesium
  • the shale inhibition properties of polyol-containing WBM can be enhanced by incorporation of potassium salts, e.g., potassium chloride, possibly in combination with gypsum.
  • potassium salts e.g., potassium chloride
  • the shale inhibition properties of even the best known potassium and polyol-containing WBM are much inferior to those of OBM.
  • the use of potassium can present waste disposal problems, as there are certain regions, e.g., the Gulf of Mexico, where the discharge of potassium to the environment is prohibited or severely restricted.
  • the use of many types of brine-based WBM can present problems in land drilling where the contamination of ground water by saline drilling waste is considered unacceptable. This waste may contain potassium or other undesirable cations or anions .
  • Shale swelling is considered as a problem not only in the oil field industry. It is encountered as clay swelling in the mining industry, where this phenomenon causes severe difficulties when dewatering the mineral tailings.
  • shale- stabilizing additive for water based drilling fluids of the following general structural formula:
  • R where R x and R 2 are H, CH. , or CH 2 -CH 3 depending on the epoxide employed, i.e. EO, PO, or BO, respectively.
  • the sum of k and 1 is in the range of 2 to preferably 25, with each individual number being equal to or larger than 1.
  • R denotes an arbitrary group, however excluding aliphatic hydrocarbyl residues with 12 carbon atoms or more.
  • R includes at least one hetero- atom such as nitrogen or oxygen.
  • the additional group R is not meant to give the novel additive a pronounced amphiphilic characteristic, as its primary use is as a shale swelling inhibitor and not as an emulsifier or a surfactant.
  • R an aliphatic hydrocarbon residue of 12 or more carbon atoms .
  • the length (index: i) of the hydrocarbon chain separating the two nitrogen atoms is preferably in the range of 1 to 10 and R' and R' ' are hydrogens or arbitrary groups, however not an aliphatic hydrocarbyl residues with 12 carbon atoms or more.
  • R' or R' ' include at least one hetero-atom such as oxygen .
  • R, to R 4 are H, CH, , or CH.-CH,, depending on the epoxide employed, i.e. EO, PO, or BO, respectively.
  • the sum of k, 1, m, and n is preferably in the range of 4 to 25, with each individual number being preferably equal to or larger than 1.
  • the length (index: i) of the hydrocarbon chain separating the two nitrogen atoms is preferably in the range of 1 to 10. In case of EDA and HDA, i is 2 and 6, respectively.
  • Such polyols and derivatives thereof are commercially available.
  • the polyol according to the present invention is preferably used as an additive in water-based drilling fluids (WBM) or in dewatering operations for mineral tailings.
  • WBM water-based drilling fluids
  • the invention concerns a drilling fluid with 0.1 to 10 weight per cent (wt%) of the novel additives as characterized before. More preferably, the novel additives are used at 1 to 5 wt%.
  • the additives in accordance with the invention provide higher levels of shale swelling inhibition in the presence of weakly hydrated cations, such as potassium, caesium, and ammonium.
  • Another advantage of the novel additives is the ability to formulate highly inhibitive water based muds without using substantial amount of such salts. In other words, inhibition can be obtained solely from using the additives in freshwater or in combination with salts containing for example sodium, calcium, or magnesium ions, rather than potassium ions. The latter advantage is particularly useful in areas where environmental concerns prohibit or severely restrict the use of saline drilling fluids.
  • An essentially potassium-free WBM is defined as having less that 3 wt% potassium content, preferably less that 1 wt%, most preferably less than 0.1 w% .
  • the oil content of the initial drilling fluid is desirable to keep the oil content of the initial drilling fluid as low as possible, i.e below 5% or even more preferable below 3%.
  • oil is naturally added to the initial mixture.
  • the initial drilling fluid with a low clay content, i.e below 5% or even more preferable below 3%, as the amount of shale swelling inhibitor which reacts with the initial clay, is no longer available for the treatment of the subterranean formation.
  • any amount of clay in the initial fluid has to be compensated by an equivalent amount of inhibitor to retain the same level of inhibition downhole.
  • novel additives can improve current methods of dewatering mineral tailings in the mining industry, as today this process is severely hampered by clay swelling .
  • the level of shale inhibition provided by different drilling fluid additives and formulations is routinely assessed by a number of laboratory techniques. Tests such as cuttings dispersion and shale swelling are suitable for the rapid screening of new additives and are widely use in the industry. A good indication of the inhibitive properties of an additive can also be obtained by a modification of the standard oilfield cuttings dispersion test. This approach is particularly suitable for screening low viscosity, water-soluble species such as polyols and fully formulated drilling fluids containing the additives .
  • a known weight of shale cuttings (approximately 20g) is added to a measured volume of test fluid (approximately 350 ml) in a container.
  • the container is rotated such that the cuttings are in a constant state of agitation in the fluid; this encourages breakdown and dispersion of the cuttings if they become softened due to interaction with the test fluid.
  • the cuttings that remain undispersed are collected, washed, dried and weighed. The recovered weight is expressed as a percentage of the original weight added to the test fluid.
  • the more inhibitive the test fluid the lower the level of cuttings dispersion and hence the higher the final recovery figure.
  • the bulk hardness of the shale treated with these polyols can be measured by pushing the shale cuttings soaked in polyol muds through a porous plate.
  • the force (torque) required to extrude the cutting is related to the efficiency of the polyol as a shale stabiliser, i.e., the highest torque values are obtained with the best shale inhibitors.
  • the examples Ml and M2 in accordance with the inventions are based on a reaction of 1 mole ethylene diamine (EDA) with 5 mole of propylene oxide (Ml) or alternatively with 3 moles of propylene oxide and 1 mole ethylene oxide (M2) .
  • the examples M3 and M4 are reaction products of 1 mole hexane diamine (HDA) with 4 moles of propylene oxide (M3) or alternatively with 5 moles of mole ethylene oxide (M4).
  • R. to R 4 are H, CH , , or CH.,-CH j/ depending on the epoxide employed, i.e. EO, PO, or BO, respectively.
  • the sum of k, 1, m, and n is preferably range of 4 to 25, with each individual number being preferably equal to or larger than 1.
  • the length (index: i) of the hydrocarbon chain separating the two nitrogen atoms is preferably in the range of 1 to 10. In case of EDA and HDA, i is 2 and 6, respectively.
  • PEG polyethylene glycol
  • PAG mixed polyethylene/polypropylene glycol
  • the average molecular weights of these materials are about 600 and 650 respectively.
  • the PAG is a random copolymer of EO and PO with an EO : PO ratio of approximately 1:1.
  • Table 1 shows the recovery of Oxford shale cuttings from solutions of de-ionised water and 5 wt% active polyol.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyethers (AREA)
  • Earth Drilling (AREA)

Abstract

La présente invention concerne un additif stabilisateur de schiste basé sur une structure moléculaire représentée par la formule (I). Cette formule comprend un polyol contenant au moins un atome d'azote, de préférence dérivé d'une diamine. L'additif peut être utilisé pour des fluides de forage à base d'eau (WBM) de façon à faciliter le processus de forage de schistes, en particulier dans des zones écologiquement sensibles.
PCT/GB1998/002377 1997-08-16 1998-08-06 Additifs stabilisateurs de schiste argileux Ceased WO1999009109A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BR9814943-1A BR9814943A (pt) 1997-08-16 1998-08-06 Fluido de perfuração e método para perfurar um poço
AU87366/98A AU8736698A (en) 1997-08-16 1998-08-06 Shale-stabilizing additives
CA002300110A CA2300110A1 (fr) 1997-08-16 1998-08-06 Additifs stabilisateurs de schiste argileux

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9717362A GB2328228B (en) 1997-08-16 1997-08-16 Shale-stabilizing additives
GB9717362.9 1997-08-16

Publications (1)

Publication Number Publication Date
WO1999009109A1 true WO1999009109A1 (fr) 1999-02-25

Family

ID=10817570

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1998/002377 Ceased WO1999009109A1 (fr) 1997-08-16 1998-08-06 Additifs stabilisateurs de schiste argileux

Country Status (6)

Country Link
AU (1) AU8736698A (fr)
BR (1) BR9814943A (fr)
CA (1) CA2300110A1 (fr)
CO (1) CO5040148A1 (fr)
GB (1) GB2328228B (fr)
WO (1) WO1999009109A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7084092B2 (en) 2003-08-25 2006-08-01 M-I L.L.C. Shale hydration inhibition agent and method of use
US7250390B2 (en) 2002-01-31 2007-07-31 M-I L.L.C. High performance water based drilling fluids and method of use
US10294410B2 (en) 2014-07-31 2019-05-21 Halliburton Energy Services, Inc. Guanidine- or guanidinium-containing compounds for treatment of subterranean formations
US10988657B2 (en) 2014-07-01 2021-04-27 Halliburton Energy Services, Inc. Clay stabilizers

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6247543B1 (en) * 2000-02-11 2001-06-19 M-I Llc Shale hydration inhibition agent and method of use
AU2014391686B2 (en) 2014-04-23 2017-09-28 Halliburton Energy Services, Inc. Clay stabilization with control of migration of clays and fines

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3086937A (en) * 1961-01-13 1963-04-23 Union Oil Co Drilling mud
US3123559A (en) * 1964-03-03 Hccjhio
FR2415134A1 (fr) * 1978-01-23 1979-08-17 Halliburton Co Solutions aqueuses gelifiees d'acides mineraux et leur application au traitement de formations souterraines

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1206580B (de) * 1964-02-15 1965-12-09 Bayer Ag Verfahren zur Herstellung flammwidriger Urethangruppen enthaltender Schaumstoffe
BE790338A (fr) * 1971-10-20 1973-04-20 Mallinckrodt Chemical Works Compositions reactives de recherche sur des echantillons biologiques, et leurs procedes de preparation et d'utilisation
US3979305A (en) * 1972-09-29 1976-09-07 Union Oil Company Of California Low fluid loss additive composition
GB8616163D0 (en) * 1986-07-02 1986-08-06 Shell Int Research Drilling fluid
US5350740A (en) * 1991-10-28 1994-09-27 M-1 Drilling Fluids Company Drilling fluid additive and method for inhibiting hydration

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3123559A (en) * 1964-03-03 Hccjhio
US3086937A (en) * 1961-01-13 1963-04-23 Union Oil Co Drilling mud
FR2415134A1 (fr) * 1978-01-23 1979-08-17 Halliburton Co Solutions aqueuses gelifiees d'acides mineraux et leur application au traitement de formations souterraines

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7250390B2 (en) 2002-01-31 2007-07-31 M-I L.L.C. High performance water based drilling fluids and method of use
US7084092B2 (en) 2003-08-25 2006-08-01 M-I L.L.C. Shale hydration inhibition agent and method of use
US10988657B2 (en) 2014-07-01 2021-04-27 Halliburton Energy Services, Inc. Clay stabilizers
US10294410B2 (en) 2014-07-31 2019-05-21 Halliburton Energy Services, Inc. Guanidine- or guanidinium-containing compounds for treatment of subterranean formations
US10655056B2 (en) 2014-07-31 2020-05-19 Halliburton Energy Services, Inc. Guanidine- or guanidinium-containing compounds for treatment of subterranean formations

Also Published As

Publication number Publication date
CA2300110A1 (fr) 1999-02-25
GB9717362D0 (en) 1997-10-22
CO5040148A1 (es) 2001-05-29
AU8736698A (en) 1999-03-08
GB2328228B (en) 2000-08-16
GB2328228A (en) 1999-02-17
BR9814943A (pt) 2000-09-05

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