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WO2014167013A1 - Procédé de fracturation hydraulique d'une formation souterraine au moyen d'urée - Google Patents

Procédé de fracturation hydraulique d'une formation souterraine au moyen d'urée Download PDF

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Publication number
WO2014167013A1
WO2014167013A1 PCT/EP2014/057180 EP2014057180W WO2014167013A1 WO 2014167013 A1 WO2014167013 A1 WO 2014167013A1 EP 2014057180 W EP2014057180 W EP 2014057180W WO 2014167013 A1 WO2014167013 A1 WO 2014167013A1
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Prior art keywords
urea
liquid
fracking
water
fraying
Prior art date
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PCT/EP2014/057180
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German (de)
English (en)
Inventor
Vladimir Stehle
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Wintershall Dea GmbH
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Wintershall Holding GmbH
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Filing date
Publication date
Application filed by Wintershall Holding GmbH filed Critical Wintershall Holding GmbH
Priority to EP14720056.2A priority Critical patent/EP2984145A1/fr
Priority to RU2015147997A priority patent/RU2015147997A/ru
Priority to CA2908791A priority patent/CA2908791A1/fr
Publication of WO2014167013A1 publication Critical patent/WO2014167013A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—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
    • C09K8/62—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

Definitions

  • the present invention relates to a method for hydraulic fraying of a subterranean formation as well as a fraying liquid (FL), which can be used in the method according to the invention.
  • At least one well is usually first drilled (drilled) into the subterranean formation.
  • fluids eg, natural gas and / or petroleum
  • at least portions of the reservoir are hydraulically fractured.
  • liquids such as suspensions or solutions, which are also referred to as fracking liquids, are introduced into the subterranean formation at a pressure in the range from 500 to 1000 MPa. This process is also referred to as “hydraulic fracturing” or “hydraulic fraying”.
  • hydraulic fracturing hydroaulic fracturing / tearing of a subterranean formation
  • hydraulic fracturing hydroaulic fracturing / tearing of a subterranean formation
  • a work string is typically lowered into the wellbore.
  • the section of the well to be hydraulically fractured is normally perforated using known technologies, e.g. B. by so-called ball perforation. This creates openings in the casing of the borehole and short channels in the surrounding rock massif.
  • the section of the well to be hydraulically fractured is typically isolated from the adjacent well sections that are not to be hydraulically fractured. For this purpose seals (packers) are used.
  • a fracturing fluid eg, a water-based gel with proppant
  • a breaking fluid passes through the perforation holes in the rock layer to be broken, which surrounds the borehole.
  • the crushing liquid is pumped at a pressure into the rock layer to be crushed, which is sufficient to separate or "break" this rock layer of the formation.
  • the crushing liquid is also referred to as fracking liquid.
  • Water-based hydraulic fraying has become increasingly important in recent years.
  • crushing liquids which contain water, gel formers and optionally crosslinkers.
  • crosslinkers leads to spontaneous gelation within a few minutes.
  • aldehydes such as glyoxal
  • the breaking fluid may contain support material such as sand. The support material should remain in the cracks formed during fraying in order to keep them open.
  • the refractive liquid may be added to other additives such as clay stabilizers, biocides or gel stabilizers.
  • a particular challenge is the gas extraction from almost dense, ie almost impermeable geological formations (tight gas reservoirs, shale gas reservoirs).
  • Hydraulic stimulation techniques in conjunction with appropriate drilling techniques should enable the economically necessary production rates of tight gas deposits and shale gas deposits and thus open up future supply reserves.
  • tight gas deposits and shale gas deposits the subterranean formations generally have a relatively high clay content.
  • the fracking water is introduced deep into the formation. As a result, the deposit is massively contaminated with water. The water causes swelling of the clay stones in the subterranean formation. This swelling reduces the permeability.
  • the economy is crucially dependent on the success of hydraulic fracking.
  • the refractive fluid thus blocks the escape of fluids such as petroleum or natural gas from the formation through the cracks and fissures in the direction of the bore. For this reason, the breaking fluid must be removed again after the hydraulic fracture from the cracks and fractures formed. The removal of the fracking liquid from the deposit matrix is particularly difficult.
  • Effective fracture length is a significant variable that limits hydrocarbon production from a given wellbore, especially for low permeability gas reservoirs.
  • the intentional removal of fracture fluid from the fracture is known as "remediation.” This term refers to the recovery of the fracturing fluid after the proppant has been deposited in the fracture seminal fluid.
  • the breaking fluid which is located in the top of the fracture, must traverse the entire length of the fracture (down to the borehole). By simply pumping back the fracturing fluid, it is usually removed only incompletely from the fractures and cracks, so that the effective fracture length is generally significantly shorter than the actual fracture length.
  • water-based gels are usually used for hydraulic fraying as crushing liquids. These are difficult to remove from the fractures due to the high viscosity.
  • so-called gel breakers are used to achieve a decrease in the viscosity of the refractive liquid used.
  • strong oxidizing agents such as ammonium persulfate are used as gel breakers.
  • solutions 5 of the oxidizing agents are subsequently pumped into the fractures for this purpose.
  • the oxidizing agent chemically degrades the gelling agent contained in the crushing fluid, as a result of which the viscosity of the crushing fluid decreases.
  • US 2010/0298177 discloses a method of treating subterranean hydrocarbon deposits and a composition used in this method.
  • the composition contains water, a water-soluble polysaccharide, one or more water-soluble salts and urea.
  • the composition can be used for matrix treatment or for the formation of fracture cracks.
  • a proppant is added to the composition to stabilize the Frackrisse.
  • no quiescent phase is introduced during which the fracturing pressure is maintained and the urea is hydrolyzed. This is disadvantageous in that the composition can emerge from the fracture cracks after it has formed. The hydrolysis of the urea in Frackrissen is therefore not guaranteed safe.
  • US 201 1/027633 discloses a method for treating subterranean formations with a eutectic mixture. For the production of the eutectic
  • an ammonium compound When mixed, an ammonium compound is reacted with a second compound selected from the group consisting of amines, amides, carboxylic acids, alcohols, and metal halides.
  • the ammonium compounds used are preferably quaternary ammonium chlorides. These can be reacted, for example, with urea.
  • fracking compositions When mixed, an ammonium compound is reacted with a second compound selected from the group consisting of amines, amides, carboxylic acids, alcohols, and metal halides.
  • the ammonium compounds used are preferably quaternary ammonium chlorides. These can be reacted, for example, with urea.
  • US 3,195,635 describes a method of forming fracture tears in a subterranean formation.
  • a composition which comprises a permanent proppant and urea prills contains.
  • the permanent proppant and urea prills are suspended in a liquid, preferably petroleum.
  • the urea Prillen are preferably coated with an oil-soluble material.
  • DE 2 933 037 A1 describes a hydraulic fracking process suitable for fraying gas-bearing sandstone formations.
  • the process comprises several stages in which crushing liquids carrying a fine support material sand of a size in the range of 0.25 to 0.105 mm are used in a sand / liquid mixing ratio of 0.48 kg / l.
  • Each stage with the support material sand is immediately followed by a corresponding stage, in which a breaking fluid without Stützmaterialsand is used.
  • a final stage injects a fracturing fluid containing a backing material sand having a size in the range of 0.84 to 0.42 mm, followed by a purging of the drill string with fracturing fluid.
  • the refractive fluid contains up to 70% by volume of alcohol to reduce the volume of water in the fracturing fluid, which is detrimental to water-sensitive clays within the formation.
  • up to 20% by volume of liquefied carbon dioxide is combined with the tails-water / alcohol mixture to further reduce the volume of water.
  • the process according to DE 2 933 037 A1 is very cost-intensive due to the large number of different stages as well as due to the alcohol and liquid carbon dioxide used as solvent.
  • the refractive liquid can not be completely removed by the method according to DE 2 933 037 A1.
  • a fracturing fluid is sequentially introduced into a borehole.
  • the refractive fluid in the individual sequences is selected such that the refractive fluid in the vicinity of the fracturing tip has a lower viscosity and / or a lower density than the fracture fluid in the vicinity of the borehole.
  • This viscosity and / or density gradient is intended to facilitate the removal of the breaking fluid from the fracturing tip.
  • the sequential method according to DE 699 30 538 T2 is likewise very complicated. Even with this method, the removal of the crushing liquid from the formed fracture tip is not guaranteed safe.
  • a method of tailoring in which the fracking liquid is converted into a gas is disclosed in WO 2008/076952.
  • liquid carbon dioxide is used as the fracking liquid.
  • the conversion of the fracking liquid to a gas is achieved by a pressure reduction in the process described in WO 2008/076952 initiated in the borehole.
  • the method of WO 2008/076952 is very expensive, since special equipment is needed to inject liquid carbon dioxide into a borehole.
  • the process is dangerous because it can lead to uncontrolled leakage of large C0 2 amounts.
  • the gaseous carbon dioxide can lead to corrosion problems in the well casing and other metallic equipment.
  • a viscous liquid is usually injected into the underground reservoir under a pressure of up to 1000 bar and pumping rates of up to 10 m 3 / min.
  • fracture fractures also known as fracture cracks
  • 2 to 5 pumps are used simultaneously.
  • up to 10 pumps can be used simultaneously.
  • a proppant is also usually pressed into the deposit together with the fracking liquid.
  • the fracture fractions formed in the hydraulic fraying have very good hydraulic conductivity, and the area of the fracture fractures can be, for example, 4000 to 120000 m 2 .
  • the properties of the fraying fluid have a very large influence on the fracking efficiency.
  • Frackliquidkeit example petroleum. Thereafter, aqueous solutions thickened by simple polysaccharides were used.
  • thickeners for example, guar gum, xanthan gum or polyacrylamides were used.
  • thickeners were used in concentrations of up to 0.95% by weight, based on the total weight of the fracking liquid.
  • crosslinkable polymers have been used for gelling the fracking liquid.
  • the viscosity of the conventionally used fracking liquids can vary at very large intervals.
  • fracking liquids containing mainly water with a minimum amount of thickener have viscosities of only about 10 cP and are mainly used for fraying shale gas deposits.
  • non-thickened water in which fine sand is suspended as a proppant is also used.
  • the methods described in the prior art for hydraulic fraying of subterranean formations are very complex. With the known methods as complete as possible removal of the fracturing fluid used for hydraulic fraying from the fractures formed is usually not guaranteed safe.
  • the object is achieved by the method according to the invention for hydraulic fraying of a subterranean formation, into which at least one bore has been drilled, comprising the method steps a) introducing a frac liquid (FL) through the at least one bore into the subterranean formation, with a pressure which is greater as the minimum local rock stress, to form fracture cracks (FR) in the subterranean formation, the fracturing fluid (FL) containing water and urea, and b) inserting a rest phase in which the hydrolysis of the urea takes place with the water of the fracking liquid (FL).
  • a frac liquid FL
  • a pressure which is greater as the minimum local rock stress
  • the actual fracture length described above is also referred to below as the actual fracture length (tFRL).
  • the effective fracture length described above will also be referred to hereinafter as the effective fracture length (wFRL).
  • the method according to the invention makes it possible to effectively improve the hydrodynamic communication between a subterranean formation and a well.
  • the Frackrisse (FR) generated by the process according to the invention have an effective Frackriss length (wFRL), which corresponds approximately to the actual Frackriss length (tFRL).
  • wFRL effective Frackriss length
  • tFRL actual Frackriss length
  • Urea converts to ammonia and carbon dioxide in the presence of water by hydrolysis according to the following equation:
  • thermohydrolysis Upon complete hydrolysis of one ton of urea, about 1200 m 3 of gases are formed.
  • gases spontaneously form in process step b) in the fracture cracks (FR) formed in process step a).
  • the carbon dioxide formed preferably dissolves in the liquid hydrocarbons contained in the subterranean formation and reduces their rheological properties.
  • the ammonia formed preferably dissolves in the water contained in the subterranean formation, for example the water contained in the fraying liquid (FL). This increases the pH of the water.
  • the dissolved ammonia has thereby a surfactant-like effect and reduces the surface tension of the water, which facilitates the removal of the water from the Frackrissen formed (FR).
  • liquid ammonia may also form under certain conditions at sufficiently high pressures in the subterranean formation.
  • the formation of gas also forces the water contained in the fraying fluid (FL) from the fracking cracks (FR) towards the borehole, which also leads to removal of the water from the fracture cracks (FR) formed. Due to the interaction of the present effects, the complex remediation of the fracture cracks (FR) formed in hydraulic fraying described in the prior art is not required or the remediation effort is at least substantially reduced.
  • process step b) the water contained in the fracking liquid (FL) is at least partially consumed.
  • the fracture cracks (FR) formed are practically “dried out.”
  • the swelling of the clay stones in the subterranean formation is largely prevented and a concomitant decrease in the permeability is prevented or at least reduced.
  • the fraying liquid (FL) removes itself practically, so that the complex and costly remediation steps described in the prior art need not necessarily be carried out in the process according to the invention.
  • the process of the present invention may be used for the development of shale gas deposits, tight gas deposits, shale oil deposits, dense-carrier oil deposits, bituminous and heavy oil deposits using "in-situ combustion", gas extraction Coal formation, coalfield downhole gasification, metal mine downhole extraction, rock depressurization and modification of stress fields in geological formations, abstraction of water from underground reservoirs, and development of underground geothermal deposits.
  • the method according to the invention can be used for hydraulic fraying of all known subterranean formations into which at least one bore has sunk.
  • the process according to the invention is preferably used in underground deposits which carry one or more raw materials. Suitable raw materials are those described above, for example natural gas, petroleum, Coal or water.
  • the terms "subterranean formation” and “subterranean deposit” are used synonymously below.
  • the process according to the invention is preferably used for the hydraulic fraying of subterranean formations which contain as raw materials hydrocarbons such as crude oil and / or natural gas.
  • hydrocarbon deposits are preferred that lead oil and / or natural gas and was drilled in the at least one hole.
  • the natural gas deposits are particularly preferred.
  • the subject of the present invention is also a process in which the subterranean formation is a natural gas deposit with a deposit permeability of less than 10 milliDarcy.
  • the method according to the invention can be used both in injection and in production wells.
  • the shape and configuration of the bore is not critical to the process of the invention.
  • the method according to the invention for hydraulic fraying can be applied in vertical, horizontal as well as in quasi-vertical or quasi horizontal bores.
  • the method according to the invention can be applied in deflected bores comprising a vertical or quasi-vertical and a horizontal or quasi-horizontal section.
  • the temperature T L of the underground deposit (subterranean formation), which is hydraulically cracked by the method according to the invention, is usually in the range of greater than 65 to 200 ° C, preferably in the range of 70 to 150 ° C, particularly preferably in the range of 80 to 150 ° C and in particular in the range of 90 ° C to 150 ° C.
  • the temperature T L is also called a reservoir temperature T L.
  • the subject matter of the present invention is therefore also a method in which the underground deposit has a reservoir temperature (T L ) in the range from greater than 65 to 200 ° C., preferably in the range from 70 to 150 ° C., particularly preferably in the range from 80 to 150 ° C and in particular in the range of 90 to 150 ° C.
  • T L reservoir temperature
  • the sinking of at least one hole in the subterranean formation is known per se.
  • the drilling holes can be made by conventional methods known in the art and is described for example in EP 09 523 00.
  • the fracking fluid (FL) contains urea and water.
  • the fracking fluid (FL) contains urea in concentrations of from 30 to 70% by weight.
  • the weight percentages of urea refer to the sum of the weight percentages of water and urea contained in the tailing fluid (FL).
  • the optionally contained proppant (SM) and other additives are not taken into account in the weight percentages of urea.
  • the weight percentages of urea thus only refer to the ratio of water and urea contained in the fraying fluid (FL).
  • the urea concentration is from 30 to 77% by weight, preferably from 50 to 67% by weight and more preferably from 60 to 77% by weight.
  • the present invention thus also relates to a process in which the fraying liquid (FL) contains 30 to 70% by weight of urea, preferably 50 to 77% by weight of urea and particularly preferably 60 to 77% by weight of urea, based on the sum of the weight fractions of water and urea contained in the fraying fluid (FL).
  • the urea in one embodiment, does not have a coating of an oil-soluble material.
  • the urea is used uncoated.
  • the ratio of water to urea in the fracking fluid (FL) is equimolar.
  • the dissolution behavior of urea in water is shown in the phase diagram in FIG.
  • the urea content in terms of the sum of the weight proportions of urea and water in the fracking liquid (FL) is given in percent by weight, in the case where the fraying liquid (FL) contains only urea and water.
  • the temperature is given in ° C, on the left vertical axis and by the dotted curve (1) the proportion of remaining after the hydrolysis of the urea residual water (RW) is given, based on the sum of the proportions by weight of urea and water in the fracking fluid (FL).
  • the dashed vertical line (2) in Figure 1 indicates the urea concentration (76.9% by weight) at which the water contained in the fracking liquid (FL) would be completely consumed in the hydrolysis of urea.
  • the proportion of remaining residual water (RW) after hydrolysis of the urea in the tailing liquid (FL) is zero.
  • urea and water in the fraying fluid (FL) were originally in equimolar amounts.
  • residual water (RW) remains after the hydrolysis of the urea.
  • the amount of the remaining Residual water (RW) as a function of the urea concentration is shown in FIG. 1 by the dotted curve (1).
  • the urea may be present in dissolved form. It is also possible to use a fracking liquid (FL) which, in addition to urea in dissolved form, also contains urea in suspended particulate form.
  • the dissolution behavior of urea is temperature-dependent. Below the crystallization temperature (T K ) is a part of the urea in the fracking liquid (FL) in particulate form.
  • the crystallization temperature (T K ) is understood to mean the temperature below which the urea initially dissolved dissolved in the fracking liquid (FL) crystallizes, so that the fraying liquid (FL) contains water, urea in dissolved form and urea in undissolved form.
  • the crystallization temperature (T K ) of the fracking liquid (FL) in FIG. 1 corresponds to the curve which separates the greyed area "solution” from the area "solution + crystals".
  • the fracking fluid (FL) may contain urea in completely dissolved form.
  • the concentration of urea and the temperature of the fracking liquid (FL) must be selected so that the pair of values of temperature and concentration in the shaded gray solution area of Figure 1.
  • the present invention thus also provides a process in which the fracking liquid in process step a) is introduced at a temperature (T FI _) which is above the crystallization temperature (T K ) and in which the urea in the fraying liquid (FL) completely in dissolved form.
  • these days can be heated.
  • the heating accelerates the dissolution of the urea used.
  • Crystallization of urea from a supersaturated aqueous solution is a relatively slow process. For this reason supersaturated solutions can be used.
  • These supersaturated solutions may, for a period of time, contain urea concentrations in completely dissolved form, which are actually present in the solution + the figure 1 lie.
  • fracking liquids (FL) which have a crystallization temperature (T K ) which is below the reservoir temperature (TL) of the subterranean formation. This ensures that the urea in the fracking fluid (FL) remains in the subterranean formation in completely dissolved form or is subsequently dissolved.
  • the present invention thus also relates to a process in which the fracking liquid (FL) has a crystallization temperature (TK) which is below the reservoir temperature (TL) of the subterranean formation.
  • the tailing liquid (FL) in process step a) is generally introduced at a temperature (T FI _) below the reservoir temperature (T L ) of the subterranean formation lies.
  • Suitable temperatures (T FI _) for the fracking liquid (FL) are, for example, in the range from 5 to ⁇ 65 ° C., preferably in the range from 10 to 60 ° C., particularly preferably in the range from 15 to 40 ° C.
  • a fracking liquid FL is used, in which part of the urea is in dissolved form and another part of the urea is in particulate, suspended form.
  • the present invention thus also provides a process in which a part of the urea in the fracking liquid (FL) is present in dissolved form and another part in particulate, suspended form
  • urea is in particulate, suspended form.
  • the urea particles can be used in powder or granular form.
  • the urea particles generally have a size in the range of 10 ⁇ m to 3 mm.
  • urea solutions such as, for example, Ad- blue® from BASF SE.
  • Ad- blue® from BASF SE.
  • these solutions can also be used directly.
  • Frackwormkeit (FL) which contains urea both in dissolved form and in particulate, suspended form, further urea can be added to this solution subsequently.
  • the urea particles are in suspended form.
  • the thickening agents described above may be added to the fracking liquid (FL). Since when pumping the tailing liquid (FL) into the subterranean formation usually strong turbulence These may also be sufficient to prevent settling of the urea particles without the use of a thickener.
  • the suspended particulate urea particles accumulate in the fracture cracks (FR) formed in process step a).
  • the interface between fracking crack (FR) and the surrounding rock acts as a filter.
  • the process is carried out analogously to the enrichment of the aluminum particles.
  • the subject matter of the present process is thus also a process in which, in process step a), at least part of the urea present in particulate, suspended form accumulates in the fracture cracks (FR) formed.
  • the urea concentration in the fracking cracks (FR) can be higher than the urea concentration of the frac liquid (FL) originally used.
  • the water contained in the fracking liquid (FL) in the fracking cracks (FR) is at least partially, preferably completely consumed.
  • the viscosity of the fraying liquid (FL) can be adjusted via the amount of urea contained in the fraying liquid (FL) in particulate, suspended form become.
  • the suspension viscosity of the fracking fluid (FL) can be adjusted here over wide intervals.
  • Tail fluids (FL) having a suspension viscosity in the range of 10 to 10 000 cP can be prepared. This makes it possible to use proppant (SM), their density or specific gravity over wide ranges vary.
  • the suspension viscosity of the fracking liquid (FL) can be adjusted individually to the respectively used proppant (SM) by the content of urea in particulate, suspended form.
  • Another factor that affects the suspension viscosity of the tailing fluid (FL) is the size of the urea particles in suspended form. The finer the urea particles which are suspended in the fracking liquid (FL), the higher the suspension viscosity of the fraying liquid (FL).
  • the mass ratio between liquid (ie, the saturated aqueous urea solution) and the urea in particulate, suspended form in the fracturing fluid (FL) may range from 100: 1 to 1: 100.
  • the fraying liquid (FL) contains large amounts of urea in particulate, suspended form, a highly viscous paste is obtained. However, this paste is still pumpable by conventional pumps in the underground reservoir.
  • the fracking liquid (FL) can also be used without proppant (SM).
  • SM proppant
  • the fraying liquid (FL) urea both in dissolved form and in undissolved form, i. contains particulate, suspended form, can be dispensed with conventional chemical additives in one embodiment.
  • the fraying fluid (FL) contains no other conventional chemical additives. As a result, a fraying liquid (FL) is obtained which manages without aggressive chemicals and is particularly environmentally friendly.
  • the present invention thus also provides a process which is characterized in that one part of the urea in the fracking liquid (FL) is in dissolved form and another part in particulate, suspended form and the fraying liquid (FL) contains no thickening agent.
  • the fracking liquid (FL) used according to the invention thus combines a multiplicity of positive effects:
  • step b The water content in Frackrissen (FR) is drastically reduced in step b), ideally the water is completely consumed.
  • Chemical additives such as so-called chemical gel breakers in the fracking liquid (FL) can be dispensed with, since the ammonia liberated in process step b) acts as a gel breaker acts and leads to a drastic reduction of the original viscosity of the tailing liquid (FL) used.
  • Urea is also an environmentally friendly product that decomposes without residue into non-toxic substances.
  • the fracking liquid (FL) may additionally contain further compounds selected from the group consisting of ammonium carbamate, ammonium carbonate and ammonium bicarbonate. These compounds can partially replace the urea contained in the fraying fluid (FL). These compounds also hydrolyze with the formation of ammonia and carbon dioxide. The hydrolysis temperature of these compounds is significantly lower than the hydrolysis temperature of the urea used.
  • Ammonium carbamate (NH 2 C0 2 NH 4 ) is readily soluble in water. The hydrolysis of the ammonium carbamate to ammonia and carbon dioxide starts at 35 ° C.
  • the carbon dioxide liberated in the hydrolysis of ammonium carbamate and the liberated ammonia catalyze the decomposition of the urea contained in the fracking liquid (FL) by increasing the pH.
  • the compounds selected from the group consisting of ammonium carbamate, ammonium carbonate and ammonium bicarbonate can thus be used as an initiator for starting the urea hydrolysis.
  • the fraying liquid (FL) may additionally contain a proppant (SM).
  • SM proppant
  • Suitable proppants are known in the art.
  • Suitable supporting agents are, for example, particulate ceramic materials such as sand, bauxite or glass beads.
  • the particle size of the proppant depends on the geometry of the fracture cracks (FR) that are to be supported. Suitable particle sizes are generally in the range of 0.15 mm to 3.0 mm.
  • SM proppant
  • propellants (SM) of relatively small particle size are selected for the natural gas deposits and proppants (SM) of larger particle size are used for petroleum reservoirs.
  • the permeability / permeability of the filler gap filled with proppant should be 10 3 to 10 8 greater than the permeability of the deposit, this ensures optimal conditions of gas or oil extraction.
  • the support means (SM) serves to keep open the Frackrisse (FR) formed during hydraulic fraying. That is, the support means (SM) prevents the Frackrisse (FR) close again when process step a) is completed and by the Fracklandaiskeit (FL) constructed hydraulic pressure decreases again.
  • the proppant (SM) must be introduced into the fracture cracks (FR) formed in process step a).
  • the proppant (SM) is therefore generally also suspended in the fraying fluid (FL).
  • the water contained in the fracking liquid (FL) serves as Stromal Transport means to transport the proppant (SM) and optionally the urea particles or aluminum particles in the Frackrisse.
  • the Rush upon. Means of transport is hereinafter also referred to as aqueous carrier liquid (WT).
  • aqueous carrier liquid water itself can be used. It is also possible to use as the aqueous carrier liquid (WT) a mixture of water and one or more organic solvents. Suitable organic solvents are, for example, glycerol, methanol or ethanol.
  • the aqueous carrier liquid (WT) serves as a means of transport, with the help of which, if necessary, the proppant (SM), the aluminum and the urea particles are transported into the fracking cracks (FR).
  • the proppant (SM) is generally present in amounts of from 1 to 65% by weight, preferably in amounts of from 10 to 40% by weight and more preferably in amounts of from 25 to 35% by weight in the fracturing fluid (FL) based on the total weight of the fraying fluid (FL).
  • the amount of proppant used (SM) depends on the reservoir properties.
  • sea water sea water, partially desalinated seawater or formation water
  • formation water is understood to mean water which is originally present in the deposit, and water which has been introduced into the deposit through secondary and tertiary production process steps, for example so-called floodwater.
  • the fraying fluid (FL) may contain aluminum.
  • the fraying liquid (FL) contains no aluminum.
  • the aluminum may be present in the fracturing fluid (FL) in amounts of from 10 to 25% by weight, based on the total weight of the fracturing fluid (FL).
  • the fraying liquid (FL) contains aluminum the aluminum is preferably used in particulate form.
  • the particle size of the aluminum is generally from 20 nm to 1000 ⁇ , preferably 20 nm to 500 ⁇ and particularly preferably 50 nm to 50 ⁇ . The particle size of the aluminum can thus be in the micrometer range ( ⁇ -aluminum) and / or in the nanometer range (n-aluminum).
  • n-aluminum aluminum having a particle size in the range of 50 to less than 1000 nm.
  • ⁇ -aluminum aluminum having a particle size in the range of 1 to less than 1000 ⁇ .
  • the subject matter of the present invention is thus also a process which is characterized in that the fraying liquid (FL) comprises a mixture of aluminum particles with a particle size in the range of 50 to less than 1000 nm (n-aluminum) and aluminum particles with a particle size in the range of 1 to less than 1000 ⁇ contains.
  • the aluminum particles accumulate in the fracture cracks (FR) formed in process step a).
  • the rock spores then act as filters.
  • the water contained in the fraying fluid (FL) penetrates into the rock spores and the aluminum particles are retained in the fracking cracks (FR).
  • only the ⁇ -aluminum particles are larger than the rock spores.
  • only the ⁇ -aluminum particles accumulate in the Frackrissen (FR). The n-aluminum particles penetrate into the rock spores together with the water.
  • the tailing fluid (FL) may contain an oxidizing agent (O).
  • Suitable oxidizing agents (O) are, for example, hydrogen peroxide or ammonium nitrate.
  • the oxidizing agent (O) is also dissolved in the aqueous carrier liquid (WT).
  • WT aqueous carrier liquid
  • Oxidizing agents (O) may be added to the tailing fluid (FL) to increase the amount of energy released in step b).
  • the oxidizing agent (O) may be present in amounts of from 0 to 50% by weight, preferably in amounts of from 1 to 10% by weight and more preferably in amounts of from 1 to 5% by weight, in the fracturing fluid (FL).
  • thickening agent (FL) may be added with thickening agents in order to increase the viscosity of the fraying liquid (FL) and to prevent the sedimentation of the optionally used urea or aluminum particles and optionally of the Prevent proppant (SM).
  • the fracturing fluid (FL) generally contains from 0.001 to 1% by weight of at least one thickening agent, based on the total weight of the fracturing fluid (FL).
  • Suitable thickeners are, for example, synthetic polymers such as polyacrylamide or copolymers of acrylamide and other monomers, especially monomers containing sulfonic acid groups, and polymers of natural origin such as glucosylglucans, xanthan, diuthane or glucan. Glucan is preferred.
  • the addition of gel breakers is not necessary since, after the temperature increase in process step b) in the fracking cracks (FR), the fraying liquid (FL) loses its viscosity.
  • the fracking fluid does not contain a thickening agent.
  • Turbulence in the bore in the implementation of the process step a) sediment the particles and the optionally used proppant (SM) only slowly, so that the addition of thickening agents is not mandatory.
  • the turbulences occurring during injection of the fracking liquid (FL) in process step a) may be sufficient, even without the use of thickening agents, in order to keep the urea or aluminum particles and optionally the proppant (SM) suspended.
  • the fracking liquid (FL) contains preferably 0.1 to 5 wt .-%, particularly preferably 0.5 to 1 wt .-% of at least one surfactant, based on the total weight of the fracking liquid (FL).
  • anionic, cationic and nonionic surfactants As surface-active components it is possible to use anionic, cationic and nonionic surfactants.
  • Common nonionic surfactants are, for example, ethoxylated mono-, di- and trialkylphenols, ethoxylated fatty alcohols and polyalkylene oxides.
  • polyalkylene oxides preferably C 2 -C 4 -alkylene oxides and phenylsubstituted C 2 -C 4 -alkylene oxides, in particular polyethyleneoxides, polypropyleneoxides and poly (phenylethyleneoxides), especially block copolymers, in particular polypropylene oxide and polyethylene oxide blocks or poly (phenylethylene oxide) and Polyethylene oxide blocks having polymers, and also random copolymers of these alkylene oxides suitable.
  • Alkylenoxidblockcopolymerisate are known and commercially z. B. under the name Tetronice and Pluronic (BASF) available.
  • Typical anionic surfactants are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 -C 12 ), of sulfuric monoesters of ethoxylated alkanols (alkyl radical: C 12 -C 18 ) and ethoxylated alkylphenols (alkyl radicals: C 4 -C 12 ) and of alkylsulfonic acids ( Alkyl radical: C 12 -C 18 ).
  • Suitable cationic surfactants are, for example, C 6 -C 18 -alkyl, alkylaryl or heterocyclic radicals, primary, secondary, tertiary or quaternary ammonium salts, pyridinium salts, imidazolinium salts, oxozolinium salts, morpholinium salts, propylium salts, sulfonium salts and phosphonium salts.
  • Examples include its dodecylammonium acetate or the corresponding sulfate, disulfates or acetates of various 2- (N, N, N-trimethylammonium) ethylparaffinkla- esters, N-Cetylpyridiniumsulfat and N-Laurylpyridiniumsalze, cetyltrimethyl ammonium bromide and sodium lauryl sulfate called.
  • the use of surface-active components in the fraying fluid (FL) lowers the surface tension of the fraying fluid (FL).
  • the flowable composition (FZ) contains no surfactants.
  • Hydraulic fraying techniques are known to those skilled in the art and briefly outlined in the introductory part of the present specification.
  • step a) the frac liquid (FL) is injected into the well at a pressure greater than the minimum local rock stress of the subterranean formation.
  • fractures and cracks which are also referred to as fracking cracks (FR) are formed in the vicinity of the bore due to the hydraulic action of the liquid pressure of the fraying liquid (FL).
  • the minimum in-situ rock stress of the subterranean formation is also referred to as the minimum principal stress. This is understood to mean the pressure necessary to form fracture tears (FR) in the subterranean formation.
  • the pressure required depends on the geological and geomechanical conditions in the subterranean formation. These conditions include, for example, rock / depth, reservoir pressure, stratification, and rock strength of the subterranean formation.
  • the pressure is increased until the formation of Frackrissen (FR) occurs.
  • FR Frackrissen
  • the pressures that are necessary for this purpose are usually in the range of 100 to 10,000 bar or 100 to 1000 bar, preferably in the range of 400 to 1000 bar, more preferably in the range of 600 to 1000 bar and particularly preferably in the range of 700 to 1000 bar.
  • the pumping rates can rise to 10 m 3 / min.
  • the fracture cracks (FR) formed in process step a) are filled with the fraying liquid (FL).
  • the fraying liquid (FL) contains a proppant (SM), this is introduced together with the urea and the aluminum particles in the Frackrisse (FR).
  • the support means (SM) prevents the Frackrisse (FR) close again after a pressure reduction.
  • Suitable devices for building up the required pressures are also known to the person skilled in the art.
  • the perforated portion of the bore which is to be hydraulically cracked in accordance with method step a) is isolated from the adjacent borehole section by means of a seal (packer).
  • the fraying fluid (FL) is usually passed through a work string into the area to be
  • a quiescent phase is introduced in which the hydrolysis of the urea proceeds.
  • the period of time for the resting phase in method step b) is generally one hour to seven days.
  • the hydrolysis of the urea preferably proceeds completely in process step b). That is, after process step b) are at least 95%, preferably at least 98%, more preferably at least
  • the fracking liquid (FL) may be under a pressure which is higher, equal to or lower than the pressure in process step a).
  • the fracking liquid (FL) may be under a pressure which is higher, equal to or lower than the pressure in process step a).
  • the fracking liquid (FL) in method step b) is also possible for the fracking liquid (FL) in method step b) to be at a pressure which is lower than the local rock stress.
  • the subject of the present invention is a method which is characterized in that the fraying liquid (FL) during the process step b) is under a pressure 40 which is at least equal to the local rock stress.
  • the fracking liquid additionally contains aluminum
  • an exothermic oxidation reaction also takes place in process step b), which additionally consumes water. Due to the released heat water can also be evaporated.
  • the exothermic oxidation reaction of aluminum with water follows the reaction equation below
  • the heat development takes place on the surface of the aluminum particles, ie at the boundary between aluminum and water. As a result, primarily the aluminum particles and then the water of the fracking liquid (FL) are heated. At temperatures of the tailing liquid (FL) below 65 ° C, the oxidation of aluminum with water (without additives) proceeds only very slowly without a noticeable increase in the temperature of the fracking liquid (FR). When the temperature of the fracking fluid (FR) is above 65 ° C, however, the oxidation of aluminum with water is fast. At these temperatures, the oxidation of aluminum with water takes place spontaneously and continues without external energy input. At temperatures above 65 ° C, no igniter is required to initiate the exothermic reaction.
  • the aluminum particles In the event that at least part of the aluminum particles is larger than the rock spores, the aluminum particles accumulate in the fracture cracks (FR) formed in process step a).
  • the rock spores act as a kind of filter.
  • the water contained in the fraying fluid (FL) penetrates into the rock spores.
  • the aluminum particles are retained at the boundary between fracking crack (FR) and surrounding rock.
  • the temperature rise in the exothermic oxidation reaction in conjunction with the hydrolysis of the urea simultaneously decompose chemical additives such as thickening agents in the fracking cracks (FR).
  • the aluminum concentration in the Frackrissen (FR) is thus significantly higher than the aluminum concentration of the used after performing process step a) Tail Fluid (FL) made on the surface.
  • the Filter solid. Enrichment effect is analogous to the enrichment of urea particles.
  • the n-aluminum particles penetrate into the rock spores together with the water contained in the fraying liquid (FL).
  • the aluminum concentration in the rock spores is usually smaller than the aluminum concentration in the fracture cracks (FR) and, moreover, usually smaller than the aluminum concentration of the topcoats (FL) produced on a daily basis.
  • the decomposition of the urea releases ammonia underground, which dissolves in the water of the fraying fluid (FL).
  • the pH of the fracking liquid (FL) increases and the oxidation reaction between aluminum and water begins spontaneously.
  • the increase in the pH usually begins after formation of the fracture cracks (FR) according to process step a).
  • the fracking liquid (FL) heats up, causing decomposition of the urea and liberating ammonia.
  • aluminum hydroxides and aluminum oxides which are not soluble in water.
  • the oxidation products (aluminum hydroxide and aluminum oxide) have a high degree of dispersion.
  • the resulting in the exothermic oxidation reaction aluminum hydroxides and alumina are also porous.
  • the oxidation products thus do not block the fracture cracks (FR) formed in process step a). Rather, the porous oxidation products act like a proppant (SM) especially for gas deposits and thus can additionally contribute to the improvement of the hydrodynamic communication.
  • SM proppant
  • Restructuring of fracture cracks (FR) is further assisted by the resulting gas and vapor pressure, which includes all components of the fraying fluid (FL), with the exception of the proppant (SM) and the oxidation products of aluminum, from the top of the fracking fracture (FR) Press towards the borehole.
  • the proppants used are at least partially rinsed out of the fracking cracks (FR) again in the remediation step. With the method according to the invention, flushing out of the support means (SM) from the fracking cracks (FR) is largely prevented.
  • the urea converts to the water contained in the fracking liquid (FL) by hydrolysis according to the following equation in ammonia and carbon dioxide: H 2 N-CO-NH 2 + H 2 O -> 2NH 3 + CO 2
  • thermohydrolysis One mole of urea and one mole of water form two moles of ammonia and one mole of carbon dioxide.
  • the hydrolysis of urea with water under the action of heat is also referred to as thermohydrolysis. From a temperature of greater than 65 ° C, the hydrolysis of urea and water proceeds sufficiently quickly to completely hydrolyze the urea and the water to carbon dioxide and ammonia in economically meaningful periods.
  • the rate of hydrolysis of urea increases with increasing temperature.
  • urea can be in process step b) increase the amount of gas and thus increase the gas pressure in Frackrissen (FR). This favors the refurbishment of fracture cracks (FR) as well as the expansion or new formation of pores in the rock adjacent to the fracture cracks (FR).
  • the subject of the present invention is therefore also a process in which the subterranean formation is an underground hydrocarbon deposit.
  • the present invention furthermore relates to a method in which the subterranean formation is a natural gas deposit with a deposit permeability of less than 10 milliDarcy.
  • the subject of the present invention is furthermore a method for hydraulic fracking of a subterranean hydrocarbon deposit which has a deposit temperature T L of> 65 ° C.
  • the reservoir temperature T L is preferably in the range of> 65 to 200 ° C, preferably in the range of 70 to 150 ° C, particularly preferably in the range of 80 to 140 ° C.
  • the fracing liquid (FL) in process step a) is preferably introduced into the subterranean formation at a temperature of the fraying liquid T FI _ (the underground hydrocarbon deposit) which is smaller than the deposit temperature T L.
  • T FI _ the underground hydrocarbon deposit
  • the fracking liquid (FL) is thus preferably used at temperatures ⁇ 65 ° C. in process step a).
  • the temperature of the fraying liquid T FI _ in process step a) is preferably in the range from -5 to 60 ° C., preferably in the range from 0 to 60 ° C., and more preferably in the range from +10 to 60 ° C.
  • the fracturing fluid (FL) is slowly heated under the effect of the temperature conditions of the subterranean formation (the underground hydrocarbon reservoir). This heating takes place in process step b) of the process according to the invention.
  • the fraying liquid (FL) reaches temperatures of> 65 ° C, whereby the hydrolysis reaction between water and urea and optionally the exothermic oxidation reaction between aluminum and water is used.
  • the present invention thus also provides a process for the hydraulic fraying of an underground hydrocarbon deposit (an underground formation) in which the fracturing fluid (FL) is introduced in process step a) at a temperature T FI _ lower than the reservoir temperature T L of the underground Hydrocarbon deposit (the underground formation).
  • the present invention is further illustrated by the following embodiments, without, however, limiting it thereto.
  • the tight gas deposit has the following parameters:
  • depth in the range of 3800 to 4100 m (TVDss, actual vertical depth less the elevation above sea level)
  • a fraying fluid (FL) with a urea concentration of 63% by weight (based on the sum of water and urea in (FL)) is used.
  • the water of the fracking liquid (FL) is heated.
  • 220 kg proppant (SM) (proppant) and 10 kg of a thickener (data per m 3 Frackstattkeit (FL)) are suspended.
  • the fracking liquid (FL) is subsequently pressed into the deposit at a pressure of about 700 to 800 bar (process step a)), whereby fracture cracks (FR) are formed.
  • the Frackrisse (FR) have widths in the range of 2 to 4 mm.
  • the fraying liquid (FL) heats up to a temperature of over 100 ° C within a period of 1 to 2 hours after the start of the introduction. This increase in temperature causes the spontaneous decomposition of the urea and the increase in the pH of the fracking fluid (FL). Part of the water contained in the fraying fluid (FL) is consumed by hydrolysis of the urea (about 75% of the water contained in the fraying fluid (FL)).
  • the reaction time is three days.
  • the remaining fracking liquid can subsequently be removed from the well by known remedial measures.
  • the production of natural gas is recovered by known techniques added.
  • the gas delivery rate is increased by carrying out the method according to the invention by 20 to 100%, compared with the initial production rate (delivery rate before carrying out the method according to the invention) increased. This is largely attributable to the fact that the method according to the invention prevents the deposit from becoming diluted, since the fracking liquid (FL) according to the invention virtually quarries itself.
  • urea concentration 32 wt .-% used.
  • This is available under the brand name "Ad-blue ®" from BASF SE, which only solidifies at temperatures in the range of -1 to -14 ° C and is therefore suitable for use in cold northern regions approx. 200 kg of proppant and additionally approx. 300 kg of urea granulate per cubic meter of urea solution
  • the total urea concentration of the fracking liquid (FL) used is thus about 60%.
  • the thickener used is a synthetic polymer.
  • the amount of the polymer is 10 kg / m 3 of the water used.
  • This fracking liquid (FL) is subsequently pressed into the subterranean formation under pressures in the range from 700 to 35 800 bar, forming fracture cracks (FR).
  • the urea granules are mechanically completely or at least partially comminuted.
  • the urea particles used are partially further dissolved or suspended in the 40 Frackwashkeit (FL). This facilitates the subsequent hydrolysis of the urea in the fracture cracks (FR) formed.
  • the fracture cracks (FR) formed in process step a) and the rock surrounding these fracture cracks (reservoir matrix) are in this case saturated with a liquid whose urea concentration is above the urea concentration of the urea solution originally used (Ad-blue®).
  • Simulation calculations and laboratory investigations have shown that the surrounding area of the dense reservoir matrix can absorb a maximum of 15% of the tailing fluid (FL).
  • the predominant amount of the fraying liquid (FL) containing the suspended proppant (SM) and the suspended urea particles remains in the fracking cracks (FR).
  • Simulation calculations have shown that the temperature of the fracking fluid (FL) rises to 1 15 to 17 C ° approximately one hour after formation of the fracture cracks (FR).
  • the concentration of urea in the fracture cracks (FR) formed is significantly higher than 60% as the urea particles accumulate in the fracture cracks (FR) formed.
  • the inserted resting phase is three days. During this time, a large part of the urea hydrolyzes in the fracking cracks (FR) as well as in the deposit matrix. Remains of the water are alkalized by the ammonia formed.
  • the remaining alkaline fracturing fluid (FL), which may contain dissolved residues, can be removed from the well by known remedial measures.

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  • General Life Sciences & Earth Sciences (AREA)
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Abstract

L'invention concerne un procédé de fracturation hydraulique d'une formation souterraine et un liquide de fracturation (FL) pouvant être utilisé dans ce procédé.
PCT/EP2014/057180 2013-04-10 2014-04-09 Procédé de fracturation hydraulique d'une formation souterraine au moyen d'urée Ceased WO2014167013A1 (fr)

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EP14720056.2A EP2984145A1 (fr) 2013-04-10 2014-04-09 Procédé de fracturation hydraulique d'une formation souterraine au moyen d'urée
RU2015147997A RU2015147997A (ru) 2013-04-10 2014-04-09 Способ гидравлического разрыва подземного пласта с использованием мочевины
CA2908791A CA2908791A1 (fr) 2013-04-10 2014-04-09 Procede de fracturation hydraulique d'une formation souterraine au moyen d'uree

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Citations (7)

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US3195635A (en) * 1963-05-23 1965-07-20 Pan American Petroleum Corp Spacers for fracture props
US3270815A (en) * 1963-09-11 1966-09-06 Dow Chemical Co Combination hydraulic-explosive earth formation fracturing process
US20100298177A1 (en) * 2009-05-20 2010-11-25 Halliburton Energy Services, Inc. Methods for treating a well using a treatment fluid containing a water-soluble polysaccharide, a water-soluble salt, and urea
US7946342B1 (en) * 2009-04-30 2011-05-24 The United States Of America As Represented By The United States Department Of Energy In situ generation of steam and alkaline surfactant for enhanced oil recovery using an exothermic water reactant (EWR)
US20110207633A1 (en) * 2008-03-26 2011-08-25 Shrieve Chemical Products, Inc. Deep eutectic solvents and applications
US20120305255A1 (en) * 2011-05-31 2012-12-06 Victor Borisovich Zavolzhskiy Method of Treating the Near-Wellbore Zone of the Reservoir
EP2537910A1 (fr) * 2011-06-22 2012-12-26 Wintershall Holding GmbH Procédé d'extraction de pétrole visqueux d'un dépôt sous-actif

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3195635A (en) * 1963-05-23 1965-07-20 Pan American Petroleum Corp Spacers for fracture props
US3270815A (en) * 1963-09-11 1966-09-06 Dow Chemical Co Combination hydraulic-explosive earth formation fracturing process
US20110207633A1 (en) * 2008-03-26 2011-08-25 Shrieve Chemical Products, Inc. Deep eutectic solvents and applications
US7946342B1 (en) * 2009-04-30 2011-05-24 The United States Of America As Represented By The United States Department Of Energy In situ generation of steam and alkaline surfactant for enhanced oil recovery using an exothermic water reactant (EWR)
US20100298177A1 (en) * 2009-05-20 2010-11-25 Halliburton Energy Services, Inc. Methods for treating a well using a treatment fluid containing a water-soluble polysaccharide, a water-soluble salt, and urea
US20120305255A1 (en) * 2011-05-31 2012-12-06 Victor Borisovich Zavolzhskiy Method of Treating the Near-Wellbore Zone of the Reservoir
EP2537910A1 (fr) * 2011-06-22 2012-12-26 Wintershall Holding GmbH Procédé d'extraction de pétrole visqueux d'un dépôt sous-actif

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