PRIOR RELATED APPLICATIONS

[0001] This application claims priority to US Serial No. 63/244,953, filed September 16, 2021, and incorporated by reference in its entirety for all purposes.

FIELD OF THE DISCLOSURE

[0002] This disclosure provides methods of testing core preservation fluids for drilling core samples and returning them to the surface in an unchanged condition.

BACKGROUND OF THE DISCLOSURE

[0003] One of the ways of studying rock characteristics is to drill and analyze a core sample from a reservoir. Similar to a drill bit, the rotary coring bit consists of solid metal with diamonds or tungsten for cutting at the reservoir rock, but unlike a drill bit, a rotary coring bit has a hollow center. The cutting apparatus thus surrounds the hollow center, called the core barrel, where the core sample is stored. The core barrel is made up of an inner and outer barrel separated by ball bearings, which allows the inner barrel to remain stationary and retain the core sample, while the outer barrel is rotated by the drill string and cuts the core. The core catcher is located within the core barrel and has finger-like apparatuses that move the core sample farther into the barrel and keep it from falling back into the well. After the core sample has been cut from the well, the drill string is raised, and the rotary coring bit, barrel and catcher are removed, and the core sample is retrieved. The drill bit is reattached, and drilling can commence again.

[0004] However, obtaining an unaltered core sample from a reservoir with these simple prior art devices remains challenging. As the core is retrieved from deep in the reservoir, the temperature and pressure decrease which allows gases to evolve out of solution and together with free gases, expand, resulting in reservoir fluids being forced out of the core. Thus, accurate sampling, especially of fluids, is difficult, if not impossible to obtain. [0005] To address this problem, the core samples are sometimes collected and sealed in a chamber, in a method known as "pressure coring". Pressure coring at least partially solves the problem by maintaining the core specimen at bottom-hole pressure — BHP — until the core fluids can be recovered. This concept, first proposed by Sewell in the 1930's, remained a "laboratory" tool until the late 1970's, but with the advent of ever improving technology, the method is much more popular now.

[0006] However, in pressure coring the core samples are contained in an inert fluid known as FC-40 aka FLUORINERT™ which was developed for electronic uses, not uses in the petroleum industry. FC-40 is a colorless, thermally stable, fully fluorinated liquid that was believed to be inert, even at reservoir temperature and pressure (RTP). With the data presented herein, we now know that it in fact solubilizes some of the lighter fractions of oil, and thus skewing the results of high pressure core analysis. The discrepancy arises from the fact that standard testing techniques are wholly inappropriate for use with a so- called “inert” fluid developed for electronic uses, as opposed to downhole uses.

[0007] This disclosure for the first time provides assays and methodology to correctly assay downhole core samples, and further develop novel inert, high density fluids for use in obtaining and analyzing reservoir core samples.

SUMMARY OF THE DISCLOSURE

[0008] FC-40 contains C5-18 perfluorocarbon chains, that are largely inert to electronics, but less so for petroleum, which contains short, medium, and long chain hydrocarbons. Table A provides the known FC-40 properties:

[0009] As is apparent, FC-40 is not particularly viscous, but is fairly dense at 1.9 g/ml. Insomuch as electronics are concerned, it is fairly inert, but as demonstrated herein, light hydrocarbons have significant solubility in FC-40, even at atmospheric conditions, and at reservoir temperature and pressure (RTP), the problem is greatly exacerbated.

[0010] Thus, what is needed in the art are test methods for correctly assaying inert fluids for downhole uses. Such assays would allow the art to develop new materials that do not dissolve light hydrocarbons but is otherwise as dense and inert to the full range of petroleum constituents, especially at RTP. In the absence of an absolute inert fluid, characterization of solubility in FC-40 and other fluids at atmospheric and at reservoir conditions will provide methods to characterize interactions within the reservoir and simulate processes under reservoir conditions.

[0011] As used herein, “brominated” or “fluorinated” means to replace one or more hydrogens with bromine or fluorine.

[0012] As used herein, “perbrominated” or “perfluorinated” is to combine with the maximum amount of fluorine especially in place of hydrogen.

[0013] As used herein, “high pressure” means higher than 1 atm, and includes all typical downhole pressures (e.g. up to and even beyond 25,000 psi).

[0014] As used herein, a “high temperature” means reservoir temperatures which are greater than 100 °F, typically about 200-400 °F in a reservoir.

[0015] As used herein “live oil” is oil containing dissolved gas in solution that may be released from the oil solution at surface conditions. Live oil must be handled and pumped under closely controlled conditions to minimize the risk of explosion or fire.

[0016] As used herein “dead oil” is oil that has been flashed to STP or ambient conditions at the surface and no longer containing very much dissolved gas. [0017] As used herein, “bubblepoint” or “bubble-point pressure” is defined as the temperature and pressure at which gas begins to break out of an under saturated oil and form a free gas phase in the matrix or a gas cap. In layman’s terms it may be thought of as the pressure at which the first bubble of gas appears at a specific temperature. The phase diagram of typical black oils shows that the bubble-point pressure could be different at different temperatures and pressures dependent upon many factors including gas concentration and oil composition. Often the oil is saturated with gas when discovered, meaning that the oil is holding all the gas it can at the reservoir temperature and pressure, and that it is at its bubblepoint. Occasionally, the oil will be undersaturated. In this case, as the pressure is lowered, the pressure at which the first gas begins to evolve from the oil is defined as the bubblepoint. In the petroleum industry, if bubble-point pressure value is mentioned without reference to a particular temperature, the temperature is implicitly assumed to be the reservoir temperature.

[0018] As used herein, “reservoir T” or “reservoir P” or “reservoir TP” or “RTP” refer to reservoir temperature, reservoir pressure, or reservoir temperature and pressure conditions at the depth the hydrocarbon is found at. If the depth of the play is significant, an average RTP within the play can be used.

[0019] As used herein, “standard TP” or “STP” is defined as a temperature of 273.15 K (0 °C, 32 °F) and an absolute pressure of exactly 105 Pa (100 kPa, 1 bar). Standard temperature and pressure in the oil industry may vary, however, as standard temperature is 15 °C and pressure may vary by state regulations. Further, many use ambient conditions in the lab instead as providing for easier experiments.

[0020] As used herein, “saturation pressure” is the pressure at a given temperature where the fluid goes into the two-phase region (from a one-phase region). The two-phase region may be influenced by gas concentration and oil composition at a given reservoir temperature and pressure. The vapor pressure of a liquid can be defined as the saturation pressure at ambient temperature. Inversely, the saturation pressure of a gas condensate is its dewpoint pressure. Saturation pressure is equivalent to bubble point pressure at a given pressure and temperature below the critical point. At temperatures above the critical point, the saturation pressure is equivalent to dew point until a single phase gas reservoir is reached at an upper temperature.

[0021] As used herein, “zero-flash” refers to flashing a live oil sample to standard conditions in a closed loop system so that nothing escapes.

[0022] The use of the word “a” or “an” in the claims or the specification means one or more than one, unless the context dictates otherwise.

[0023] The term “about” means the stated value plus or minus the margin of error of measurement or plus or minus 10% if no method of measurement is indicated.

[0024] The use of the term “or” in the claims is used to mean “and/or” unless explicitly indicated to refer to alternatives only or if the alternatives are mutually exclusive.

[0025] The terms “comprise”, “have”, “include” and “contain” (and their variants) are open-ended linking verbs and allow the addition of other elements when used in a claim.

[0026] The phrase “consisting of’ is closed, and excludes all additional elements.

[0027] The phrase “consisting essentially of’ excludes additional material elements, but allows the inclusions of non-material elements that do not substantially change the nature of the invention.

[0028] Any claim or claim element introduced with the open transition term “comprising,” may also be narrowed to use the phrases “consisting essentially of’ or “consisting of,” and vice versa. However, the entirety of claim language is not repeated verbatim in the interest of brevity herein.

[0029] The following abbreviations may be used herein:

BRIEF DESCRIPTION OF THE DRAWINGS

[0030] FIG. 1.1. CCE experiment on live oil at 303 °F. Relative volume as a function of pressure.

[0031] FIG. 1.2. CCE experiment on live oil at 303 °F. Oil compressibility as a function of pressure.

[0032] FIG. 2.1. CCE experiment of live oil/FC-40 fluid system at 303 °F. Relative volume as a function of pressure.

[0033] FIG. 2.2. CCE experiment of live oil/FC-40 fluid system at 303 °F. Oil/FC-40 compressibility as a function of pressure.

[0034] FIG 3. PICTURE 1 : Oil before contact with FC-40.

[0035] FIG. 4. PICTURE 2: Initial contact with FC-40.

[0036] FIG. 5. PICTURE 3 : Oil / FC-40 initial interface (no mixing). [0037] FIG. 6. PICTURE 4: Oil / FC-40 dispersion layer (no mechanical mixing).

[0038] FIG. 7. PICTURE 5: Oil / FC-40 dispersion layer 2 (no mechanical mixing).

[0039] FIG. 8. PICTURE 6: Initiate mechanical mixing.

[0040] FIG. 9. PICTURE 7: Oil / FC-40 interface fluid change during mechanical mixing.

[0041] FIG. 10. PICTURE 8: Oil / FC-40 interface after aging overnight.

[0042] FIG. 11. PICTURE 9: Oil / FC-40 interface at saturation pressure.

[0043] FIG. 12. PICTURE 10: Oil / gas interface at saturation pressure.

[0044] FIG. 13. PICTURE 11 : FC-40 after flashing from cell.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0045] To further advance our sealed cell development work, an experiment was devised to understand liquid and gas phase hydrocarbon solubilities in FC-40 (FLUORINERT™). Previous accepted industry standards for oil solubilities in FC-40 (e.g., none) were established at atmospheric temperature and pressure conditions. However, due to the nature of the sealed cell acquisition and laboratory procedures, FC-40, reservoir samples and associated hydrocarbons are in contact with each other at pressures and temperatures in great excess of those used to establish the original solubility standards. Thus, we suspected that the prior data is not accurate.

[0046] To understand the temperature and pressure impact on hydrocarbon solubilities in FC-40 a number of tests at RTP were conducted, as described below. In these experiments, Eagle Ford Hunsaker B9 live oil samples with reconditioned FC-40 fluid were studied at RTP of this play (5000 psia, 303 °F). In general, the live oil is characterized before and after equilibration with FC-540 or other test fluid, and changes in the characterization indicate that the test fluid is not inert. In particular, one might see changes in density, components, bubble point, dew point and the like. In this instance, we determined that FC- 40 is not inert — solubilizing some of the lighter oil components and thus changing each of these parameters. [0047] It is common to use recycled FC-40 in the coring apparatus due to the high expense of FC-40 and in reliance on the assumption that it is inert. Depending on the program, we have requested virgin FC-40 to be used, but our initial proof of concept work was performed with used FC-40. Preparing the FC-40 as described herein ensures if the experiment is undertaken with recycled fluids the full solubility of oil in the FC-40 is measured.

[0048] FC-40 fluid obtained from previous pressure core projects was subjected to vacuum and heat overnight to remove any previously solubilized hydrocarbon components. The FC-40 fluids from different core samples were combined and then analyzed for chemical constituency with gas chromatography with carbon disulfide (CS2) solvent with an internal standard.

[0049] To obtain the composition of live oil, we flash to ambient conditions, measure the gas, the dead oil composition, and the gas to oil ratio (GOR) and calculate the live oil composition from that by adding the gas components back in. The same can be done after equilibration of test fluid, such as FC-40, at RTP and the results compared to determine if the test fluid is indeed inert.

[0050] The bubble point pressure is determined by an experiment called the constant composition expansion or CCE. The CCE is done on the live oil before and after RTP equilibration with FC-40. If FC-40 is truly inert, the bubble point should not change. To perform a CCE, a known volume of live oil from a cylinder is transferred to a PVT cell. The live oil or live oil and FC-40 mixture are stabilized for 24 hours at RTP conditions. Then, an isothermal depressurization of at least 9 pressure steps is undertaken above saturation pressure. Below the bubble point pressure, a similar isothermal depressurization down to maximum expansion of the PVT cell volume is conducted. Cell volume is recorded at each pressure step. Saturation pressure is determined visually (herein we used bubble point) and graphically from the CCE experiment.

[0051] In more detail, these experiments are described as follows: FC-40 AND LIVE OIL MIXTURE STUDY

[0052] The following experimental procedures were followed, and corresponding results are included herein:

[0053] 1. Measure the composition of live oil (including weight % of the components) and density (HPHT densitometer) at 5000 psi and 303 °F (RTP).

[0054] 2. Perform a CCE test to determine bubble point of live oil at RTP.

[0055] 3. Flash the live oil and measure the density of the remaining oil.

[0056] 4. Clean the cell and charge it with 310 cc of reconditioned FC-40 and 60-cc live oil.

[0057] 5. Mix.

[0058] 6. Equilibrate the mixture at RTP.

[0059] 7. Measure the volume of the oil phase and FC-40 phase at RTP.

[0060] 8. Perform another CCE experiment to determine bubble point of the equilibrated

FC-40/oil system at RTP.

[0061] 9. Displace the FC-40 and flash a portion of the remaining oil phase to STP or ambient conditions to measure amount and composition of gas that leaves solution.

[0062] 10. Displace the remainder of the oil phase and measure density (HPHT densitometer) and composition of the oil at STP.

[0063] The reservoir fluid composition is reported in Table 1. It had a bubble point of 3547 psia at 303 °F (Table 2). Constant composition expansion at 303 °F indicated a fluid density of 0.5302 g/cc at the saturation pressure (bubble point) of 3547 psia (Table 3), and average total compressibility of 4.227 x 10 ^-5 psi ^-1 (Table 4). Table 5 reports a constant composition expansion experiment performed on the reservoir fluid/FC-40 mix where a bubblepoint of 617 psia (shown in Table 6) at 303 °F was measured. The oil phase volume shrank from 60 cc at 5015 psig to 20.30 cc after mixing. FIG. 4-7 (Pictures 2-5) show the rapid diffusion of the oil into the FC-40 phase before mixing. [0064] The 20.3 cc of oil remaining was displaced and its composition measured as reported in Table 7. The FC-40 was displaced and flashed to ambient conditions; a gas phase was recovered and its composition measured and an oil phase that separated from the FC-40 also had its composition determined.

[0065] The composition of the oil components that solubilized into the FC-40 was estimated in Table 8 by combining the gas and oil phases that came out of the FC-40 at ambient conditions by material balance. The material balance around the entire experiment (Table 9) indicates that the live oil composition reported in Table 8 should have more light ends. This is probably due to the fact that light hydrocarbons have significant solubility in FC-40 even at atmospheric conditions. FIG. 13 confirms that the light hydrocarbons are more soluble in FC-40, leaving the heavier components in the oil phase.

[0066] Since the current standard so-called “inert” fluid (FC-40) (Table 10) removes light hydrocarbons, it would be beneficial to find a better inert fluid for downhole uses at RTP. The ideal fluid should be dense, and inert to hydrocarbons, as well as not preferentially solubilize any of the hydrocarbon components. In addition, the solution should be reasonably safe to use, and not contribute to environmental degradation or present safety hazards.

[0067] To that end, we will test silicon-based molecules that are fully substituted with fluorine, or silicon-based compounds with hydrophobic R groups, including siloxanes (SiH ₃ (OSiH ₂ )nOSiH ₃ ), or silicones.

[0068] Silicone fluids can be discussed in two categories: inert fluids and functional fluids.

Polydialkyl-, arylalkyl- and fluoroalkylsiloxane polymers and co-polymers, carrying no reactive (under-the-use conditions) groups, belong to the first category and may be tested as described herein.

[0069] A possible test fluid is (CH ₃ ) ₃ -Si-O-Si(CH ₃ ) ₂ -O-Si(CH ₃ )(R)-O-Si(CH ₃ ) ₃ where (R) is hydrophobic.

[0070] Another test fluid might be a fluorosyl:

[0071] In fact, many fluorosyls are available for testing herein, including Fluorosil 2010, Fluorosil H418, Fluorosil JI 5, Fluorosil LI 18, Fluorosil OH C7-F, Silwax F, Fluorosil OH ACR C7-F, Fluorosil TFP 1000, Fluorosil TFP 10,000, Fluorosil TFP D7, and the like.

[0072] High Temperature Silicones such as Dynalene 600 or SYL THERM (a polydimethylsiloxane liquid) may also be tested.

[0073] Another option is phenylsiloxane-dimethylsiloxane copolymer and diphenylsiloxane-dimethylsiloxane copolymers. As phenyl groups replace methyl groups in a polysiloxane, several changes occur. Oxidation resistance, thermal stability, and shear resistance are enhanced.

[0074] Modified silicones that have a higher density and chemical resistance and are potential candidates include:

[0075] Brominated hydrocarbons may also work, and mercury compounds or mercury containing mixes in the manner similar to that described herein. Any of the above described or similar compounds that test as inert in the herein described tests will be used as core sampling inert fluids and/or core storage inert fluids.

[0076] Suitable compounds may not be 100% inert, but the ideal solution would be 95% inert or better for the time it takes to collect core samples and test them — e.g., no more than 5% change in content. Thus, the inert fluid should be at least 95% inert when tested with core at RTP for at least 6 hours, preferably at least 12, or even 24, 36 or 48 hours. Even more preferred is a 96, 97, 98, or 99% inertness.