Classifications

• • E—FIXED CONSTRUCTIONS
  • E21—EARTH OR ROCK DRILLING; MINING
  • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
  • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
  • E21B43/25—Methods for stimulating production
  • E21B43/26—Methods for stimulating production by forming crevices or fractures
• • 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
• • 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
  • C09K8/03—Specific additives for general use in well-drilling compositions
  • C09K8/035—Organic additives
• • 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
  • C09K8/66—Compositions based on water or polar solvents
  • C09K8/68—Compositions based on water or polar solvents containing 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
  • C09K8/60—Compositions for stimulating production by acting on the underground formation
  • C09K8/84—Compositions based on water or polar solvents
  • C09K8/86—Compositions based on water or polar solvents containing organic compounds
  • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
  • C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • E—FIXED CONSTRUCTIONS
  • E21—EARTH OR ROCK DRILLING; MINING
  • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
  • E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
  • E21B21/003—Means for stopping loss of drilling fluid
• • E—FIXED CONSTRUCTIONS
  • E21—EARTH OR ROCK DRILLING; MINING
  • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
  • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
  • E21B43/25—Methods for stimulating production
  • E21B43/26—Methods for stimulating production by forming crevices or fractures
  • E21B43/267—Methods for stimulating production by forming crevices or fractures reinforcing fractures by propping
• • 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
  • C09K2208/26—Gel breakers other than bacteria or enzymes

Definitions

• This invention relates to a dispersion solution for drilling used for extracting underground resources such as petroleum, natural gases and the like relying on a well drilling method such as rotary drilling method or riserless drilling method, and relates to a method of extracting underground resources using the dispersion solution.
• Well drilling methods such as rotary drilling method and riserless drilling method as well as hydraulic fracturing method have now been widely employed for extracting underground resources.
• the rotary drilling method consists of forming the well by drilling while refluxing the mud and forming a filter cake called mud wall on the wall surfaces of the well using a finishing fluid blended with a water loss-preventing agent.
• the cake maintains the chute walls stable, prevents the chute walls from collapsing and reduces friction to the fluid flowing through the well.
• the hydraulic fracturing method consists of pressurizing the fluid filled in the well to form cracks (fractures) in the vicinities of the well to thereby improve permeability in the vicinities of the well (for easy flow of the fluid) in an attempt to increase the effective sectional area through which the resources such as oils and gases flow into the well and, therefore, in order to improve productivity of the well.
• the water loss-preventing agent that is added to the finishing fluid there are chiefly used calcium carbonate or various kinds of salts in a granular form.
• use of the water loss-preventing agent brings about such problems that it becomes necessary to conduct a treatment with acid to remove it, or the grains enter into the stratum and, specifically, into cracks in the stratum to block the flow of gases. That is, the water loss-preventing agent stays clogged in the stratum from where the resources are to be extracted hindering the production.
• the fluids used in the hydraulic fracturing method can be grouped into a fracturing fluid and a filler, the fracturing fluid being used so as to permeate into the vicinities of the well under the application of a high pressure while the filler being used in order to block the flow passage in the well.
• a viscous fluid like jelly gasoline As the fluid for use in the hydraulic fracturing method, there has heretofore been used a viscous fluid like jelly gasoline.
• the shale gas or the like gas has now been extracted from the shale layer that exists in relatively shallow places and by taking the effects on the environment into consideration, it is becoming a common practice to use an aqueous dispersion solution obtained by dissolving or dispersing a polymer in water.
• a known example of the polymer is polylactic acid (see a patent document 1).
• the polylactic acid is a substance that exhibits hydrolysable capability and biodegradable capability, and, even if it remains under the ground, is decomposed by water or enzyme in the ground and does not adversely affect the environment. Further, the water that is used as a dispersant, too, can be considered to be far from affecting the environment as compared to gasoline or the like.
• the well is filled with the aqueous dispersion solution in which the polylactic acid has been dispersed as the fracturing fluid and is pressurized so that the polylactic acid permeates to the vicinities of the well.
• the polylactic acid undergoes the hydrolysis and loses the form of the resin. Therefore, spaces (or cracks) form in the portions through where the polylactic acid had been permeated accounting for an increase in the space of the well into which the resources can flow.
• the polylactic acid also works as a water loss-preventing agent. That is, by forming the filter cake in the well by using the finishing fluid that is blended with the polylactic acid as the water loss-preventing agent, it is made possible to suppress the water contained as a dispersion medium in various fluids used in the subsequent steps of extraction from permeating into the ground too much. Therefore, the polylactic acid offers an advantage of minimizing a change in the environment in the stratum. Besides, no treatment with acid is necessary since it decomposes in the ground.
• the lactic acid which is decomposed from the polylactic acid is an organic acid. As the polylactic acid decomposes, the lactic acid is released. The lactic acid corrodes the shale layer and accelerates the shale layer to become porous.
• the polylactic acid undergoes the hydrolysis relatively quickly at temperatures of not lower than 100° C.
• its rate of hydrolysis is small at temperatures of lower than 100° C. If used for extracting, for example, the shale gas from under the ground where the temperature is low, therefore, the efficiency of extraction becomes poor and improvements are desired.
• the polyglycolic acid too, has been known to be useful as a biodegradable resin. Besides, its hydrolysable capability is higher than that of the polylactic acid; i.e., the rate of its hydrolysis at a temperature of, for example, about 80° C. is considerably larger than that of the polylactic acid and it can be effectively used to substitute for the polylactic acid. At temperatures of not higher than, specifically, 80° C. and, more specifically, not higher than 60° C., however, the rate of hydrolysis of the polyglycolic acid becomes very small. Besides the polyglycolic acid is considerably expensive as compared to the polylactic acid.
• an object of the present invention to provide a dispersion solution for drilling which exhibits a highly hydrolysable capability at temperatures of as low as 80° C. or lower and, further, as low as 60° C. or lower, which is obtained by dispersing an inexpensive hydrolysable resin material in an aqueous medium, and is used as a finishing fluid for the well drilling method or is used as a fracturing fluid or as a filler for extracting underground resources by the hydraulic fracturing method.
• Another object of the present invention is to provide a method of extraction by using the above dispersion solution for drilling.
• a dispersion solution for drilling obtained by dispersing, in an aqueous medium, a polyoxalate as the hydrolysable resin material.
• a method of extracting underground natural resources through a well formed by drilling comprising the step of introducing the dispersion solution described in claim 1 into under the ground with pressure to hydrolyze the hydrolysable resin material in hot water of not lower than 40° C.
• the polyoxalate (specifically, polyethylene oxalate) used as the hydrolysable resin material being dispersed in the aqueous medium is considerably inexpensive as compared to the polyglycolic acid and, besides, is very highly hydrolysable and shows a very highly hydrolysable capability even in a low temperature range of not higher than 60° C. (e.g., at a temperature of around 50° C.) as demonstrated in Examples appearing later.
• the dispersion solution for drilling of the present invention can be effectively used as a fracturing fluid, as a filler or as a water loss-preventing agent in the finishing fluid that is used for extracting shale gases that are, in many cases, produced from the regions close to the ground surface where the temperature is about 50° C.
• fracturing fluid as a filler or as a water loss-preventing agent in the finishing fluid that is used for extracting shale gases that are, in many cases, produced from the regions close to the ground surface where the temperature is about 50° C.
• microorganisms are not losing their activities and the polyoxalate is allowed to exhibit its biodegradable function to a sufficient degree, which is a great advantage of the present invention.
• the dispersion solution for drilling can be used, for example, as the fracturing fluid. If the well is filled with the dispersion solution and is pressurized, the hydrolysable resin material permeates to the vicinities of the well. Even if the temperature in the ground is low, the hydrolysable resin material undergoes the hydrolysis in short periods of time. Therefore, spaces (cracks) of a pillar structure can be formed in the portions to where the resin material has permeated making it possible to improve the drilling efficiency for extracting, for example, the shale gas.
• the hydrolysable resin material in the dispersion solution also works as a filler to block the flow passage in the well and fills in the well, but subsequently undergoes the hydrolysis, alleviating the problem of clogging caused by the sedimentation of the filler and, therefore, enabling the production efficiency to be improved.
• the acid formed by the hydrolysis of the hydrolysable resin material accelerates the gelation in the well causing the fluid to become highly viscous. This enables the solution to effectively permeate into the vicinities of the well as the fluid is introduced therein with pressure.
• the gel is decomposed (viscosity decreases) with the acid formed by the continuing hydrolysis and, therefore, the fracturing fluid is effectively recovered.
• the filter cake which consists of solid components (water loss-preventing agent) such as calcium carbonate and the like formed on the wall surfaces of the well can be decomposed with the acid formed by the hydrolysis of the hydrolysable resin material eliminating the need of subsequently conducting the treatment with acid and, therefore, making it possible to quickly recover the water loss-preventing agent.
• the hydrolysable resin material (solid component) in the dispersion solution by itself works as the water loss-preventing agent. Namely, the filter cake consisting of the solid component prevents the loss of water from the well (prevents the water from permeating into the ground). After the passage of a predetermined period of time, the cake undergoes the hydrolysis eliminating, as a matter of course, the need of any special treatment with acid, and can, thereafter, be recovered.
• the dispersion solution for drilling of the present invention is a dispersion solution obtained by dispersing the hydrolysable resin material in the aqueous medium and can, as required, be blended with known additives that are used for drilling or hydraulically fracturing the wells.
• the present invention uses a polyoxalate as the hydrolysable resin material.
• the resin material polymerized with the oxalic acid as at least one monomer is referred to as the polyoxalate.
• the polyoxalate is a polyester derived from the oxalic acid and a polyhydric alcohol, and is, usually, obtained by an ester interchange polymerization of a dialkyl oxalate with the polyhydric alcohol.
• the acid released from the polyoxalate has a pH (25° C.) of not more than 3 in an aqueous dispersion solution thereof of a concentration of 0.005 g/ml. If mixed into the water, the polyoxalate undergoes the hydrolysis to release oxalic acid.
• the oxalic acid serves as a hydrolyzing catalyst to further accelerate the hydrolysis.
• the polyoxalate exhibits a very high hydrolyzing capability and undergoes the hydrolysis to a very high degree even in a low-temperature range of not higher than 80° C. and, further, not higher than 60° C. as demonstrated in Examples appearing later.
• examples of the polyhydric alcohol to be reacted with the oxalic acid include ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, dodecanediol, neopentyl glycol, glycerin, pentaerythritol, sorbitan, bishydroxyethyl terephthalate, bisphenol A, polyethylene glycol and cyclohexane dimethanol.
• the polyoxalate may be blended with known additives such as plasticizer, heat stabilizer, photo stabilizer, antioxidant, ultraviolet ray absorber, flame retardant, coloring agent, pigment, filler, parting agent, antistatic agent, perfume, lubricant, foaming agent, antibacterial/antifungal agent, nucleating agent and the like.
• additives such as plasticizer, heat stabilizer, photo stabilizer, antioxidant, ultraviolet ray absorber, flame retardant, coloring agent, pigment, filler, parting agent, antistatic agent, perfume, lubricant, foaming agent, antibacterial/antifungal agent, nucleating agent and the like.
• the polyoxalate may be a copolymer that uses two or more kinds of polyhydric alcohols so far as its highly hydrolysable capability is not impaired, or may be the one that uses a carboxylic acid component other than the oxalic acid and lactone in small amounts as copolymerizable components.
• carboxylic acid used as the copolymerizable component there can be exemplified:
• dicarboxylic acids such as decanedicarboxylic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid and anthracenedicarboxylic acid, and esters thereof;
• hydroxycarboxylic acids such as glycolic acid, L-lactic acid, D-lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, manderic acid, and hydroxybenzoic acid.
• lactones there can be exemplified glycolide, caprolactone, butylolactone, valerolactone, propiolactone and undecalactone.
• the homopolymers or copolymers of the above polyoxalate can also be used being mixed together, as a matter of course.
• the most desirable polyoxalate is a polyethylene oxalate formed from the oxalic acid and the ethylene glycol.
• the above-mentioned polyoxalate should have a suitable degree of molecular weight from the standpoint of its permeability into the ground and its function as a filler when it is used as the fracturing fluid.
• the polyethylene oxalate should, usually, have a weight average molecular weight in a range of 5,000 to 1,000,000 and, specifically, 10,000 to 500,000.
• the polyoxalate is formed, by forming means known per se., into pellets, granular material, pulverized material as obtained by pulverizing the films, or into fibers or the like, and is dispersed as the hydrolysable resin material in water.
• the polyoxalate in order to decrease the cost, can be used as the hydrolysable resin material being blended with any other inexpensive hydrolysable resins in amounts in a range in which they do not hinder the above-mentioned excellent hydrolysable capability of the polyoxalate or, concretely, in such amounts that the hydrolysable capability of not less than 40% is maintained as measured by a method described later in Examples (e.g., in amounts of not more than 60 parts by weight per 100 parts by weight of the polyoxalate).
• hydrolysable resins there can be exemplified polylactic acid, polyhydroxyalkanoate, polycaprolacone, polybutylene succinate, cellulose acetate and thermoplastic starch, which can be used in the form of copolymers or blends. From the standpoint of cost, however, the polylactic acid is most desired.
• the polyoxalate may be, further, blended with a water-absorbing polymer such as polyvinyl alcohol or CMC to suppress the hydrolysis at room temperature and improve the stability thereof so that it can be handled more easily when used in the form of a fluid (fracturing fluid or filler) for the hydraulic fracturing method.
• a water-absorbing polymer such as polyvinyl alcohol or CMC
• the hydrolysable resin material comprising the polyoxalate is, usually, made present in an aqueous dispersion solution in an amount of 0.01 to 20% by weight and, specifically, 0.01 to 10% by weight from the standpoint of smoothly executing the hydraulic fracturing and quickly forming the cracks based on the hydrolysable resin material.
• the aqueous dispersion solution in which the above hydrolysable resin material is dispersed can be blended with known additives that are used in the well drilling method or the hydraulic fracturing method.
• the aqueous dispersion solution can be blended with water-soluble polysaccharides (gelling agent) such as guar gum or chitosan as a viscosity-imparting agent or as a gelling agent, or can be blended with sand as a proppant (supporting agent) so that cracks formed by the hydraulic fracturing will not be clogged.
• gelling agent water-soluble polysaccharides
• sand as a proppant (supporting agent)
• the aqueous dispersion solution can be, further, blended with a surfactant for dispersing the hydrolysable resin material and, further, with an acid, an alkali or an enzyme in a suitable amount to suitably accelerate the hydrolysis of the hydrolysable resin material.
• the additives may be added in such amounts that permit the hydrolysable resin material to be dispersed in the above-mentioned amount in the aqueous dispersion solution without hindering properties such as hydrolysable capability of the hydrolysable resin material (polyoxalate).
• the dispersion solution for drilling in which the hydrolysable resin material is dispersed is introduced with pressure into the underground so that the hydrolysable resin in the dispersion solution is hydrolyzed at a temperature of not lower than 40° C.
• the dispersion solution as the fracturing fluid, it is allowed to extract the desired underground resources.
• a vertical shaft is formed by drilling down to the stratum where the desired underground resources may be present. Next, the drilling is conducted in a horizontal direction to form a horizontal hole to thereby form the well.
• the thus formed well is filled with the dispersion solution for drilling containing the proppant described above, and is pressurized to execute the fracturing. Due to applying the pressure, the hydrolysable resin material and the proppant permeate into the vicinities of the horizontal hole and where the hydrolysable resin material undergoes the hydrolysis and extinguishes forming pillar structures. The remaining dispersion solution is sucked and, thereafter, the underground resources such as gases and oils are recovered.
• the hydrolysable resin material When the hydraulic fracturing is conducted by using the dispersion solution for drilling of the invention as the fracturing fluid, the hydrolysable resin material quickly decomposes even at a temperature of about 60° C. or lower enabling the hydraulic fracturing to be efficiently conducted in short periods of time. Besides, by using the dispersion solution for drilling in a temperature range where the enzyme does not lose its activity, the hydrolysable resin material exhibits its biodegradable property to a sufficient degree.
• the hydrolysable resin material contained in the dispersion solution of the invention can also be used, for example, as a proppant (support material).
• the proppant can be formed from the hydrolysable resin material by suitably adjusting the molecular weight and the like of the hydrolysable resin material and forming it in sizes that can be used as the proppant . Then the proppant enters into the cracks formed in the vicinities of the well and works to maintain the cracks while the resources are being extracted. After the extraction, the proppant hydrolyses and can be easily recovered.
• the hydrolysable resin material can, further, be used as a plug, a filler or a break down material.
• PEOx polyethylene oxalate
• the temperature therein was elevated stepwise to 170° C. to 190° C. to conduct the reaction for 7 hours under a reduced pressure of 0.1 to 0.2 kPa. Since the viscosity has increased, the reaction product was taken out.
• the polymer that was taken out was granulated by using a crusher, and was dried in vacuum at 110° C. for 4 hours so as to be crystallized to thereby obtain PEOx pellets.
• the obtained polymer possessed a weight average molecular weight of 70,000, a melting point of 180° C. and a glass transition temperature of 35° C.
• the polylactic acid (PLA) was fed to a biaxial extruder (ULT Nano 05-20AG manufactured by Technovel Co.) and was melted at 205° C. to prepare pellets thereof so as to be used as a sample hydrolysable resin material.
• the polylactic acid was 4032D manufactured by Natureworks Co.
• a piece of pellet prepared above was added to 10 ml of a dispersant in a 25-ml vial which was then stored still at each of the temperatures. After stored for 4 days, the pellet was taken out, dried in a vacuum drier heated at 60° C. for 4 hours, measured for its weight and was measured for its ratio of decomposition. The ratio of decomposition was calculated according to the following formula,
• Ratio of decomposition (initial weight ⁇ weight after decomposed)/initial weight ⁇ 100
• distilled water and guar gum aqueous solution aqueous solution containing 0.7 wt % of guar gum
• the PEOx pellets As pellets of the hydrolysable resin material, there were used the PEOx pellets prepared above. Namely, the PEOx pellets were dispersed in dispersion media of temperatures (decomposition temperatures) shown in Table 1, and the above hydrolysis test was conducted to measure their ratios of decomposition (Experiments 1 to 6). The results were as shown in Table 1.
• the PLA pellets prepared above were dispersed in dispersion media of temperatures shown in Table 1 like in the above Experiments. The results were as shown in Table 1.
• hydrolysable resin materials there were used crystallized powders obtained by freeze-pulverizing the PEOx pellets and the PLA pellets prepared above.
• the PEOx contained in the dispersion solution for drilling of the present invention effectively works as a filler, undergoes the hydrolysis with the passage of time after having been filled in the well and easily collapses therein due to the pressure in the well.
• the PEOx can be used as a support for holding cracks formed in the vicinities of the well. After having extracted the resources, the PEOx quickly undergoes the hydrolysis and can be easily recovered together with water in the well.
• the aqueous solution of oxalic acid was once gelled at 70° C. and lost fluidity but, after 24 hours have passed, has resumed fluidity showing a specific change in the properties. It was, therefore, learned that if there is used, as a fracturing fluid, a dispersion solution containing a gelling agent and a hydrolysable resin that releases oxalic acid upon the hydrolysis, then cracks can be formed due to the fracturing in the stage where the solution undergoes the gelling. Thereafter, the dispersion solution resumes the fluidity with the passage of time; i.e., the fracturing fluid can be recovered without using a gel breaker.
• the PLA is not hydrolyzed at 70° C., no lactic acid is released therefrom, the pH of the solution does not decrease and, as a result, chitosan that is a gelling agent does not dissolve, and the liquid is not gelled.
• the PEOx hydrolyses at 70° C., releases the oxalic acid and, therefore, behaves like an oxalic acid-containing aqueous solution. It will, therefore, be understood that the dispersion solution for drilling of the present invention that contains the PEOx, can be gelled in a low-temperature range and can be used as a fracturing fluid that necessitates no gel breaker.

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• 2013
  • 2013-08-01 JP JP2013160064A patent/JP6183039B2/ja active Active
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