PATENT APPLICATION FOR

APPLICATIONS OF SPECTRAL FINGERPRINTING OF HYDROCARBONS AND

OTHER ORGANICS

[0001] RELATED APPLICATION DATA

[0002] The present invention claims priority of U.S. Provisional Patent Application Serial No. 62382761, filed 09/01/2016, of U.S. Patent Application Serial No. 15255123, filed September 1, 2016, and of U.S. Patent Application Serial No. 15694732, filed September 1, 2017, with all three applications herein incorporated by reference.

[0003] BACKGROUND OF THE INVENTION

[0004] 1. Field of the Invention

[0005] The present invention relates to methods, apparatus and products for measuring the distribution of aromatics and other molecules in hydrocarbons and other substances, for example, certain steroids in blood samples. In another aspect, the present invention relates to methods, apparatus and products for oil and gas operations, for environmental applications, and for forensic and legal applications. In even another aspect, the present invention relates to methods, apparatus and products for oil and gas upstream applications, for oil and gas midstream applications, for oil and gas downstream applications, for environmental applications, and for forensic and legal applications. In still another aspect present invention relates to methods, apparatus and products for oil and gas upstream applications such as exploration, fracturing shale laterals, surface logging, enhanced analysis of wireline logs, analyzing old cores, reservoir modeling and reservoir description; for oil and gas midstream applications such as pipe lines, rail tank cars and ocean tankers; for oil and gas downstream applications such as custody transfer, quantified separation of merged crude into its constituent parts, detection of fraudulent additions to crude, detection of bad or wrong crude and knowing what crude and how much was produced by which operator as part of comingled crude; for environmental applications such as filling station tanks, oil spills on land, beaches, and subsea, water wells, soil around chemical plants, restaurants, etc., analyzing fracturing flowback to quantify hydrocarbon content, remediation, testing of water and drill cuttings to see what should be treatment and disposal options; and for forensic and legal applications, such as custody transfer and to allocate responsibility. [0006] 2. Brief Description of the Prior Art

[0007] There are many patents related to analyzing samples, the following of which are merely a non-exhaustive few.

[0008] U.S. Patent No. 5,589,349 issued December 31, 1996 to Shinzaki et al.discloses a method of enzymatic analysis utilizing a color-development signal amplification system associated with enzymatic cycling of NAD-NADH interconversion in the presence of dehydrogenase and its substrate, wherein the dehydrogenase is selected from the group consisting of alcohol dehydrogenase derived from Zymomonas and amino acid dehydrogenase derived from thermophilic microorganisms is disclosed. The use of alcohol dehydrogenase derived from Zymomonas provides an extremely higher detection sensitivity than that in the conventional method. The use of amino acid dehydrogenase derived from thermophilic microorganisms improves reliability of the method for a longer period of time than that in the conventional method.

[0009] U.S. Patent No. 5,858,644 issued January 12, 1999 to Chen discloses a method for detecting an analyte in a sample uses both the specificity of an enzymatic reaction and the separation power of capillary electrophoresis. In general, the method comprises: (1) subjecting a first aliquot of the sample to an analytical technique such as capillary electrophoresis, which generates a first output such as an electropherogram; (2) reacting a second aliquot of the sample in an enzyme-catalyzed reaction converting the analyte into a product, the product being detectable by the analytical technique; (3) subjecting the second aliquot to the analytical technique to generate a second output; (4) in the case of electrophoresis, measuring the absorbance of the first and second outputs (electropherograms) as a function of migration distance along the electropherogram at at least one wavelength at which either the analyte or the product absorbs to produce a first absorbance scan and a second absorbance scan; and (5) comparing the first absorbance scan with the second absorbance scan to detect the analyte. The reaction can involve a coenzyme and the analytical technique can be directed to the coenzyme. Alternatively, at least two enzymes can be used, the first enzyme generating a first product that is then acted upon by the second enzyme.

[00010] U.S. Patent Application Publication No. 2006/0154328 published July 13, 2006 by Bruce et al., relates to ionic liquids and their use as solvents in biocatalysis. According to a first aspect of the invention there is provided a method of carrying out an enzyme-catalysed reaction comprising providing a liquid reaction medium which comprises an ionic liquid including an ion which comprises a functional group selected from the group consisting of alkenyl, hydroxyl, amino, thio, carbonyl and carboxyl groups, providing in the liquid reaction medium an enzyme and a substrate for the enzyme, and allowing reaction of the substrate to occur.

[00011] U. S. Patent Application Publication No. 2010/0143995 published July 10, 2010 by Erdner-Tindal et al., discloses a process for fermentive preparation of alcohols and recovery of product using liquid-liquid extraction, wherein at least one ionic liquid is used as the extractive solvent.

[00012] In spite of the teachings of the prior art, there is a need in the art for improved methods, apparatus and products for analyzing samples. [00013] SUMMARY OF THE INVENTION

[00014] According to one non-limiting embodiment of the present invention there is provided a method of obtaining a spectra on a hydrocarbon containing sample, that may include (A) Contacting the sample with an ionic liquid to create a prepared sample, and may also include (B ) Processing the prepared sample through a spectroscopic system to obtain a spectra corresponding to the sample, wherein the spectra is suitable for determining the presence of and identity of any organic materials present sample. The sample may comprise soil, fluids, plants, drill cuttings, drilling mud, cores, water, blood, food, formation tester samples, or combinations thereof.

[00015] Other non-limiting embodiments are described below in this patent specification.

[00016] DETAILED DESCRIPTION OF THE INVENTION

[00017] Without being limited to theory, the inventors believe that the aromatic make up of crude oil is undoubtedly a product of the deposited organic and inorganic materials that make up its source rock and the post depositional history of this source rock, further augmented by the mineralogy and fluid content of the reservoir compartment to which it migrates. Over time, Brownian motion would tend to distribute this aromatic pattern uniformly throughout the compartment. So it is not surprising that samples of oil from the same compartment would have the same distribution of aromatics, nor that these distributions would vary from compartment to compartment.

[00018] Again, without being limited to theory, the inventors propose, and their initial studies indicate that this is true, not only for natural hydrocarbons, but for refined products. Moreover, not only does each reservoir have a unique distribution of aromatics but so does each compartment of the reservoir.

[00019] Quick Spectra ¹ ™ Process.

[00020] One non-limiting embodiment of the present invention provides the QuickSpectra ^' process. [00021] The QuickSpectra™ process may include mixing a measured amount of ionic liquid (or other liquid solvent and reactant) with a measured amount of sample. Non-limiting examples of suitable ionic fluids include l-Ethyl-3-Methylimidazolium trifluoromethanesulfonate, 1-Butyl- 3methylimidazolium hexafluorophosphate, 1-Ethyl- 3methylimidazolium Hexafluorophosphate, and [A1C13] [HN222] [A12C17] in a 3: 1: 1 ratio. For drill cuttings, the drill cutting(s) may be cleaned first with the ionic liquid, and then a single drill cutting may have new ionic liquid added to cover it, and then be crushed, so that the entire hydrocarbon content contained within is exposed to the ionic liquid for chemical reaction. The ionic liquid may have been calibrated and referenced before being added to the drill cutting(s) or drill cutting(s) to be crushed. This process may also be used on soil or side- wall or cores obtained from downhole and/or stored at the surface. This process may also include decanting a measured amount of the resulting fluid. This process may also include passing this fluid through a spectroscopic system. This process may also include applying a multivariate analysis processing to the spectrum (identify, quantify, classify). The process may also include adding this information to a database with time, date, and GPS stamp that the analysis was done. This process may also include maintaining the database so that results from each multivariate analysis are compared to fluids within the searchable database. Any information that goes into the database will have come from prescribed and recorded information about the IL (ionic liquid which had been calibrated and referenced with the identified spectroscope). This method may further include reporting kind, concentration, and/or fingerprint class.

[00022] In the practice of the present invention, usually the IL (ionic liquid) process has been used before crushing, and a single drill cutting will be selected for extraction of hydrocarbons contained in its interior. Then usually the IL will be added before crushing so that every bit of hydrocarbon will be tested. That is because this is a quantitative measurement as well as a qualitative measurement of pure fluids from downhole that is still contained within the formation (drill cutting(s)) as the fluid existed downhole. If this is not possible, then the entire process will take place within a closed container so that no hydrocarbon escapes.

[00023] Note that in the practice of the present invention, some ILs may be designed so as to also detect other things such as H2S in the surrounding drilling mud and in the drill cutting as well. This is clean and pure formation fluid, likely more clean and pure than that by a formation tester, even one with a focused probe such as an MDT tool. That is because when formation testers set the doughnut packer against the formation and lower the pressure behind the packer to pump fluid into the MDT tool and fluid into the flow lines and into the sample cylinders, drilling mud filtrate from the wellbore is also pumped around the packer, through the probe and into the flow lines and thus the fluid has some hydrocarbon contamination possibly even from another well. While the guard probe (focused probe), gets a cleaner sample faster than a conventional probe, the probe region sees the drilling mud filtrate first and it and the flow lines and thus the sample become contaminated immediately even possibly from a previous setting of the tool. There is no way to clean the MDT or any other formation tester downhole. Furthermore, all formation testers must deal with any invaded fluids from the wellbore when trying to get a sample from behind the mudcake.

[00024] Conventional formation testers, even conventional focused probes, cannot sample without mudcake so they would not be run at all. But there are always drill cuttings. Since in the practice of the present invention the drill cutting has been cleaned of all hydrocarbons including that contained in any pore throats and channels, when the drill cutting is crushed, only pure formation fluid is obtained. While the sample is small, it is more representative of the hydrocarbons contained in the reservoir than that from a formation tester and the QuickSpectra TM test and procedure of the present invention yields a qualitative fingerprint, with quantitative results of hydrocarbon present, as described in the cuttings document.

[00025] Random sampling of individual drill cuttings contained within a given sample can give statistical confirmation that the sample is representative of formation fluid from a given depth. The database will also identify any hydrocarbon which has previously been seen from a drill cutting, even if taken from another bulk fluid sample.

[00026] Care may also be given to controlling the sampling process. Certainly, data is just data, but data plus analysis is information. Because the present invention may provide real or near real- time information, it can be used, to control the sampling process.

[00027] It should be noted that drilling is a continuous process and the QuickSpectra™ process of the present invention should also be thought of as a continuous process. The present invention allows for plotting of quantitative fluid gradients as a function of depth and get statistics that will identify clusters and plotting contour charts that are obtained from the multivariate analysis and the learning that comes from randomly testing several samples of drill cuttings from each bulk sample. The present invention allows for providing feedback to the drillers regarding how their drilling mud is circulating. This should make it possible to further control the drilling process including mud pump rates as well as the direction and speed of the drilling. This will be the first time that fluids information is being used in the drilling and sampling process to pinpoint and optimize fracturing.

[00028] For example, immediate feedback of the presence or non-presence of hydrocarbons or the change of sample's fingerprint could be immediately used by the driller to change the direction of drilling.

[00029] An environmental example would be to control the direction of an autonomous submersible. Our equipment is small enough to be contained in a submersible and the fingerprint and concentration for hydrocarbon could be used, to follow a plume of oil to its source.

[00030] The present invention allows for not only unique classification of the hydrocarbon but also determines its concentration in rock, dirt, and other fluids. This allows numerous new applications in the drilling, producing, transporting and refining of crude oil. On the other side of the coin, it provides onsite, real-time formation sampling, detection, quantifying, remediation, and forensic level assignment

[00031] The present invention provides methods, apparatus and products for measuring the distribution of aromatics in hydrocarbons, specifically for the applications described herein. One non-limiting embodiment is in the form of a small, highly portable manual system that produces results on site, in near-real-time. The portable system is based on chemo- spectroscopic system that mixes the sample with ionic liquids (ILs) or other fluids or powders to rapidly change the aromatics in the sample into chromophores in the visible and UV range. This mixture is then presented to a miniature spectroscope that produces a digital spectrum unique to the sample. This spectrum may be sent to a multi-variate analysis system that compares it with the spectra of previously processed data.

[00032] In another non-limiting embodiment, the present invention provides an automatic system that emulates the manual process, but is needed for short sampling duty cycles or for use in inaccessible or dangerous locations such as the ocean floor or a highly contaminated site.

[00033] In even another non-limiting embodiment, the present invention provides methods, apparatus and products for measuring the distribution of aromatics and other molecules in hydrocarbons and other substances, for example, certain steroids in blood samples.

[00034] Upstream Applications.

[00035] The present invention may be utilized in various upstream applications, such as exploration, fracturing shale laterals, surface logging, enhanced analysis of wireline logs, analyzing old cores, reservoir modeling and reservoir description.

[00036] Exploration applications will generally include testing of soils, fluids, and/or plants for presence of hydrocarbons. After such testing, a determination is made as to whether the fingerprints are new or match those of nearby wells.

[00037] Fracturing shale laterals, vertical drilling, may include obtaining pure samples of hydrocarbons within the formation by bringing the formation sample to the surface in a drill cutting and chemically treating and identifying hydrocarbons, while preserving some pure drill cuttings for further PVT type of microanalysis of fluids as well as geological analysis and integration of geological and fluids analysis, and determining hydrocarbon zones, their fingerprint, and their concentration. And may further include detecting presence and concentration of condensates or other hydrocarbons in the drilling fluid that indicate that the hole condition is underbalanced and mud weight such as barite should be added to stop well production and/or well blowout. And may further include determining the presence and concentration of kerogen.

[00038] Fracturing shale laterals, lateral drilling, may include determining the presence or non- presence of hydrocarbon at the sample point; using data obtained during vertical drilling, to give feedback to driller on whether drilling is in the target zone or not; using fingerprints obtained during vertical drilling to detect the presence of a new hydrocarbons; and/or determining the presence and concentration of kerogen.

[00039] And finally, for fracturing shale laterals, the present invention may include analyze flowback to quantify hydrocarbon content.

[00040] Surface Logging may include regular sampling of drilling mud; prevention of blowouts by detecting and quantifying condensates in drilling mud; and/or fluid analysis of the surface and interior of cuttings and sidewall cores. [00041] Enhanced Analysis of Wireline Logs may include obtaining formation tester samples; depth matching and correcting wireline logs; and/or merging fluid and rock information.

[00042] The upstream portion of the present invention may also include analyzing old cores and old side-wall cores, fluids, and drill cuttings and adding these to the database.

[00043] Upstream applications may also include Reservoir Modeling/Description where fluids information is added to any known reservoir models and simulations and integrated with the geological and seismic information.

[00044] Midstream Applications

[00045] The present invention may be utilized in various oil and gas midstream applications, such as oil and gas midstream operations, pipe lines, rail tank cars and ocean tankers. Essentially, the present invention is utilized to identify what is being transported and to trace where it came from and information forwarded to where it is going. All this resulting information may be added to the data base.

[00046] Downstream (Refinery Or Sea Port) Applications

[00047] The present invention may be utilized in various oil and gas downstream applications, such as custody transfer, quantified separation of merged crude into its constituent parts, detection of fraudulent additions to crude, detection of bad or wrong crude and knowing what crude and how much was produced by which operator as part of comingled crude. [00048] Environmental Applications

[00049] The present invention may be utilized in various environmental applications, such as filling station tanks, oil spills on land, beaches, and subsea, water wells, soil around chemical plants, restaurants, etc., analyzing fracturing flowback to quantify hydrocarbon content, remediation, testing of water and drill cuttings to see what should be treatment and disposal options.

[00050] Forensic and Legal Applications

[00051] The present invention may be utilized in various forensic and legal applications, such as such as custody transfer and to allocate responsibility. This may include sampling Area Water Wells to obtain a Contour Map for Each Spectral Fingerprint. This may also include sampling Oil Spills to obtain a Contour Map for Each Spectral Fingerprint. This may also include determining accountability for Offshore Oil Spills and pollution in water and on land and responsibility for cleanup operations. This may also include determining accountability for pollution of birds, fish, oyster beds, food for people and animals.

[000521 Automatic Mud Sampler (AMS

[00053] Some embodiments of the present invention may include an automatic sampler. Generally, this is a mechanism that on command, will collect a sample of the mud returning from the borehole while drilling.

[00054] The AMS may be attached either in-line or clamped on return mud pipe. The AMS may collects and divert a small sample of the drilling mud returning from borehole. The AMS may record sample data. [00055] The AMS may provide a unique sample ID which includes date and time the sample was taken is created and attached to any subsamples of the sample and any component parts extracted from these subsamples. It should be understood that a variety of data may be recorded and attached to the ID. This data may include the date and time of acquisition, the driller's depth and other depth related data, the sample's temperature, and any other desired data.

[00056] The AMS may cool the sample if necessary or desired. The AMS may de-gassed if necessary or desired. With the AMS, the sample may be homogenized (if necessary or desired) so that any sub- sample is a faithful representative of the total sample.

[00057] With the AMS, the sample will be divided into any desired number of parts. As a non- limiting example, if divided into three parts, the first part may be diverted for geophysical analysis, the second part may be analyzed "as is" with a spectroscopic system, and, the third part may be sent to a fluid/solid separator which outputs three components: Cuttings, Fines and Fluids.

[00058] Itis believed by the inventors that one (of many) unique features of the present invention, is an automated process for evaluating formation fluid that is contained in cuttings and fines (which the inventors believe no prior art process that has been automated has ever included). Prior art devices/processes have always addressed only testing of fluids in drilling mud, and have not used ionic liquids and they have addressed only VIS ranges (excluding UV and IR ranges) and have used separate extractants and catalysts that are powders and require extenuated mixing of the powders. Their automation method or apparatus will not work and further is not definitive for analyzing clean samples downhole formation fluids.

[00059] In the practice of the present invention, once the process is automated, the information may also be fed automatically to the driller via the driller's "dashboard" to make it possible to adjust mud pump rates and choice of drill bits and mud motors to optimize drilling mud circulation. Further, additional multivariate analysis will make depth matching with drilling information more accurate.

[00060] Chain of Custody ( O

[00061] Various non-limiting embodiments of the present invention also relate to chain of custody. When performing a sampling task, it is necessary for scientific and legal reasons to maintain and store complete and accurate records of the samples and their analysis products. The CoC is a process using hardware and software to insure all processing products associated with each individual sample of the task is preserved and accessible.

[00062] According to the present invention, the basics components of chain of custody may include that the sampling task is given a unique ID, and pertinent/desired information about the overall sampling task is recorded. Further, each sample of the task may be assigned a unique ID. Further, basic data about the sample, such as date, time, and location information may be recorded.

[00063] Even further, for chain of custody, a sample may be subdivided into subsamples which are to be submitted to different analyses. The present invention anticipates that physical containers may be needed for the sub- samples and may be uniquely labeled. Further, state of the physical process applied to a subsample may be recorded and stored. Further, the result of the analysis may be ID'ed and stored. Even further, a feedback system may be included whereby information is immediately/timely reported to an automatic controller, the appropriate decision- makers, e.g., the driller, the corporate team, etc.

[00064] Sorting Fluid/Solid Separator (¥SS^

[00065] While the present invention may employ any suitable fluid/solid separator, as another embodiment, the present invention also provides such a device which may be utilized if desired.

[00066] The fluid/solid separator (FSS) of the present invention, is a device whose purpose is to separate solids by size from a fluid solid mixture. When used in the sampling process it will separate cuttings and fines (and possibly mud particles) from the drilling fluid. The fluid is forced through a series of flexible filters that remove smaller and smaller solids, resulting in an array of size sorted solids that are then flushed into a removable array of compartments, one for each size range.

[00067] When used in the drilling process it will separate cuttings and fines from the drilling mud. The sorted solids will be used in the geophysical analysis. When used in environmental remediation it will be separating soil, sand and gravel from any fluids. [00068] Aerial & Oceanic Surveys

[00069] The present invention may also include aerial or oceanic surveys. Air samples collected by aircraft or water samples collected by watercraft are processed on board to obtain fingerprints of hydrocarbons or other chemicals present in the immediate locality of the recorded GPS coordinates of the sample. Target compounds can be detected, categorized. When survey is complete, curvilinear, areal and volumetric maps of concentration can be constructed via Responsibility Mapping. The aircraft or water craft may include drone vehicles.

[00070] Data collection may include 1, 2, and 3 dimensional (full-bore) array sampling in air, water or other fluids. In such sample, 0-D: sample a single point, 1-D: sample points along the curve, such as plume of contaminant, 2-D: sample an array of points on a surface, and 3-D: sample an array of points within a solid.

[00071] Any patents, patent applications, publications, articles, books, journals, brochures, cited therein, are all herein incorporated by reference.

[00072] While the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which this invention pertains.

[00073] Further, in addition to the claims below, there are many other inventions described in the present application above that may be claimed at some future point.