Earth boring – well treating – and oil field chemistry – Earth boring – Contains organic component
Reexamination Certificate
1998-07-13
2003-04-08
Tucker, Philip (Department: 1712)
Earth boring, well treating, and oil field chemistry
Earth boring
Contains organic component
C507S261000
Reexamination Certificate
active
06544933
ABSTRACT:
This invention concerns drilling fluids, particularly water-based drilling fluids.
BACKGROUND OF THE INVENTION
Drilling fluids are used in well drilling operations, eg during drilling of oil and gas wells. During drilling, 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 addititives. 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. 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. 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 that 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.
Much effort has been put into improving the performance of WBM relative to shales, namely improving the level of so called shale inhibition of WBM. Various chemical additives have been incorporated in WBM in attempts to improve shale inhibition. In particular water soluble glycols or polyols (ie. molecules containing more than one hydroxyl groups) are widely used for this purpose, typically being added to WBM in amounts in the range 3 to 10% by weight. 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 copolymer with an EO:PO ratio of about 1:1. See, for example EP 0495579, U.S. Pat. No. 4,830,765, U.S. Pat. No. 4,172,800. For further discussion of this subject see, for instance, The Society of Petroleum Engineers Reports SPE 25989 (Reduced Environment Impact and Improved Drilling Performance With Water-Based Muds Containing Glycols) and SPE 28818 (Water Based Glycol Drilling Muds—Shale Inhibition Mechanisms) and also Schlumberger Oilfield Review, April 1994, pages 33 to 43 (Designing and Managing Drilling Fluid).
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.
A second, but minor, contribution to inhibition is observed with currently available EO:PO polymers. Here, the authors provide evidence of interactions between adjacent polyol molecules adsorbed on the clay surfaces. These interactions are independent of the concentration and composition of the aqueous salt solution and, since they are absent in the PEG and n-butanol ethoxylate molecules, they assume them to be due to the intermolecular interactions between mildly hydrophobic methyl groups in the PO portions of the EO:PO copolymers. This interaction is sufficient to make EO:PO polymers mildly inhibitive to shales in distilled water, where molecules such as PEG and AET rarely show any degree of inhibition.
The shale inhibition properties of polyol-containing WBM can be enhanced by incorporation of potassium salts, eg potassium chloride, possibly in combination with gypsum. However, the shale inhibition properties of even the best known potassium and polyol-containing WBM are much inferior to those of OBM. Further, the use of potassium can present waste disposal problems, as there are certain regions, eg. The Gulf of Mexico, where the discharge of potassium to the environment is prohibited or severely restricted. In addition, the use of potassium-containing WBM can present problems in land drilling where the contamination of ground water by potassium-containing drilling waste is.considered unacceptable.
It has now been found that the shale inhibition properties of WBM can be improved by use of novel polyol additives in the form of reaction products of polyhydroxyalkanes (also known as alditols) and alkylene oxides.
SUMMARY OF THE INVENTION
According to the present invention there is provided a water-based drilling fluid comprising as additive a reaction product of a polyhydroxyalkane and alkylene oxide.
The polyhydroxyalkane may be linear or branched and may include -up to 20 carbon atoms. The polyhydroxyalkane is preferably based on a monosaccharide, conveniently being a molecule such as glycerol, erythritol, threitol, ribitol, sorbitol, mannitol and galactitol. The currently preferred polyhydroxyalkane is sorbitol.
The alkylene oxide conveniently comprise ethylene oxide (EO), propylene oxide (PO) and/or butylene oxide (BO). Mixtures of alkylene oxides may be used.
Reaction products of polyhydroxyalkanes and alkylene oxides may be readily produced by polymerisation reactions, such as base catalysed polymerisations. Such products are obtainable commercially from a number of sources, including Dow Chemical, ICI and Hoechst.
The additive comprises a polyhydroxyalkane with at least one alkylene oxide chemically linked at one or both ends thereof, preferably at both ends forming generally symmetrical molecules. The number and nature of the alkylene oxide units is not critical provided the molecule is not too viscous, is at least partially soluble in aqueous fluids and has suitable foaming characteristics. Viscosity, insolubility and foaming tend to increase with increasing molecular weight, so larger numbers of EO units can be tolerated than is the case for PO and BO units. The additive conveniently comprises up to 30 EO units (generally 15 linked linearly to each end of the polyhydroxyalkane), or smaller numbers of PO units, BO units, of mixtures of EO, PO and/or BO in any ratio.
Good results have been obtained with additives including Sorbitol+18EO, Sorbitol+9PO, Sorbitol+4EO+6BO, Sorbitol+6EO+6BO, or Sorbitol+6BO.
A mi
Balson Terence George
Craster Bernadette
Crawshaw John Peter
Reid Paul Ian
Menes Catherine
Mitchell Thomas O.
Schlumberger Technology Corporation
Tucker Philip
Wang Bill
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