Method for quantitative analysis of core samples
BACKGROUND OF THE INVENTION 
     This invention relates to the field of quantitative analysis of earth samples, particularly to earth samples of the kind typically obtained in the process of exploration for or production of oil and gas. As oil and gas wells are drilled, it is common practice to obtain samples of the earth at different depths of interest in the well, such samples being generally termed core samples in the industry. Core samples are subjected to numerous tests and analyses in an effort to learn as much as possible about the makeup and characteristics of the earth formations in the zones of interest. 
     One of the items of interest concerning core samples that is of great interest to geologists is the mineral content of the sample. Knowledge of the mineral content yields valuable information in classifying the type and characteristics of the earth layer in question. In this regard it is vital for the geologist to know not only which particular minerals are present, but in what quantities, or proportions. 
     In the past, quantitative analysis of core samples have been a time consuming and expensive process. The technique most commonly used in the industry has been x-ray diffraction analysis or &#34;XRD&#34; XRD is for the most part capable of yielding satisfactory results when carried out by highly trained personnel. However, the method is time consuming, requiring from several hours to days to complete, and is correspondingly expensive. Therefore, there has long been a need in the oil and gas industry for a rapid, inexpensive method of making a quantitative determination of the mineral composition of core samples. This invention fulfills that long felt need. 
     SUMMARY OF THE INVENTION 
     The present invention discloses a method whereby Fourier-transform infra-red spectroscopy may be employed to obtain quantitative mineral analysis of core samples. Samples of core materials are prepared in accordance with the steps of the method and the infra-red response of the sample is determined. The response is compared to the responses of known minerals to determine the quantities of each mineral component in the sample. 
     DESCRIPTION OF PREFERRED EMBODIMENTS 
     Although not limited thereto, the invention is chiefly directed to the analysis of core samples obtained from the earth in connection with oil and gas exploration and production. Such samples are taken from boreholes in the earth, and may be taken from oil or gas producing formations or from exploratory wells which have not yet produced oil or gas. Depending upon the sample gathering technique employed, the core material may be about 3 inches in diameter and perhaps several feet long. Frequently smaller samples are extracted from the larger sample once it has reached the surface, the smaller samples being frequently referred to as &#34;plugs&#34;. These plugs are generally about 1 inch or less in diameter and perhaps 1.5-2.0 inches long. Other samples may be obtained from the sidewalls of the borehole, these samples being of a size similar to that of the plugs just described. The analytical techniques described herein may also be applied to drill cuttings, that is, the tailings that result from drilling. Such cuttings are not normally referred to as core samples, but for purposes of brevity, the term core samples as used in this application is intended to include both sidewall core samples and drill cuttings in addition to conventional cores. 
     The portion of the core sample to be analyzed is cleaned to remove any hydrocarbons that might be present. Various core cleaning methods may be used such as toluene solvent extraction or CO 2  cleaning. These cleaning methods are well known in the art and further description of them is not thought to be required. 
     The next step is to reduce the particle size of the sample until the sample particles are of a uniformly fine size. This can be accomplished by grinding in any manner that will produce the required particle size, which is to obtain an average particle size of less than one micron with no particles larger than 2 microns. We have found that these small particle sizes are essential to accurate results. If the particles are too large, such as larger than about 10 microns, various scattering and diffraction effects occur which may cause extremely broad peaks in the sample spectrum. It is possible to correct for the broad peaks through the use of special software filtering techniques, but the problem can be avoided by using the proper particle size in the sample. We prefer to begin by crushing a few grams of the sample in a mortar and pestle until the largest particle size is less than 500 microns. This pre-grinding step may not be required when the sample is initially unconsolidated such as certain tar sand samples. We then place about one gram of the crushed material in about 5 milliliters of isopropyl alcohol and grind in an agate grinding mill, such as a McCrone Micronising Mill manufactured by McCrone Research Associates, Ltd. of London, England, and grind for approximately 15-25 minutes, preferably about 20 minutes. Fluids other than isopropyl alcohol can be used, including water, but the alcohol is preferred. Its viscosity aids in allowing the material to cling to the agate rollers for better grinding, and its volatility shortens the time required to drive it out of the material after grinding. 
     At the completion of grinding the sample the liquid is poured into a watch glass and dried in a vent hood until all of the liquid carrier is evaporated. A small amount of the dried sample, preferably about 1-3 milligrams is placed in a small capsule with approximately one gram of potassium bromide. The capsule is then agitated or shaken to ensure complete mixing of the sample material and the KBr. It has been found that a dental amalgamator is suitable to provide the desired mixing although we prefer to use capsules made from abrasion resistant metal in place of the plastic capsules that are sometimes provided with such equipment. The use of plastic capsules can cause some sample contamination and affect the final results. 
     The proportion of sample to KBr is chosen in accordance with the sensitivity of the spectrometer utilized. The final sample or pellet will have different absorbance/transmittance values depending upon the concentration of sample material to KBr in the pellet. Preferably the pellet should fall in the range of about 0.3 to 2.0 maximum absorbance units, where 1 absorbance unit equals 10% transmittance and 2 absorbance units equals 1% transmittance; that is, absorbance units are equal to log 10  (100/t) where t is the percent transmittance. 
     After mixing, we prefer to place the capsule containing the mixture in a drying oven at about 65° C. to drive off any residual moisture in the material. Depending upon laboratory conditions of humidity and the like, this particular step may not be required but can in some circumstances improve overall results. 
     Approximately 200 milligrams of the mixed and dried material is weighed out and placed in a pellet preparation device of the type commonly used to prepare samples for infra-red spectrometric work. We prefer o use a pellet press made by Fred S. Carver, Inc. of Menominee Falls, Wis., specifically for preparation of infra-red spectrometer wafers or pellets. The press places the sample material under high pressure in a die and produces a coherent thin wafer like disk, commonly referred to as a pellet, which is sized for the analytical instrument employed. The press is equipped with a KBr die with gas chromatograph fraction collector, available from Spectra-Tek Co., Stamford, Conn. This produces a pellet 13 millimeters in diameter. 
     The pellet is loaded into an infra-red spectrometer with Fourier transform capability, such as the Infra-red Fourier Transform Spectrometer (FTIR) spectrometer made by Perkin-Elmer Company of Norwalk, Conn. The spectrometer is operated in its usual fashion, which involves directing a coherent infra-red beam about 8 millimeters wide through the sample pellet and capturing the resultant energy spectra, which will of course be determined by the amounts of infra-red energy absorbed and transmitted by the sample within certain wavelengths of interest. 
     We prefer to collect spectral data in the range of about 5000 wave numbers to about 400 wave numbers, that is, from about 2 microns to about 25 microns in wavelength. The instrument provides a digital output corresponding to the percent transmittance of the pellet sample for each wavelength of interest, where 100% transmittance would indicate a pure KBr sample pellet. Percent transmittance less than 100% at a particular wavelength indicate that the sample pellet has absorbed energy at those wavelengths. The precise wavelengths at which energy is absorbed is dependent upon the material, and therefore the material can be identified by its own spectral pattern. The amplitude or intensity of the signal at particular wavelengths is indicative of quantity. 
     The spectrometer produces a digitized signal which is provided via a data link to a digital computer, which can be a micro-computer, commonly referred to as a personal computer or PC. 
     Pure samples of minerals expected to be encountered in this kind of testing are first tested to establish a data base. The characteristic spectra of each pure substance is stored in the memory of the computer. The computer may then compare the wave number spectra and amplitude of unknown materials with those of the known materials in its memory and from such comparison produce a direct read-out of both the qualitative and quantitative makeup of the unknown core sample material. 
     In order for the method of the present invention to produce accurate quantitative results it is necessary that the comparison of the spectra of the unknown sample with those of pure component materials stored in memory be extremely precise. The need is especially critical when working with more complex mixtures. That is to say, a particular curve or spectra matching technique may be sufficient when only one or two component materials are present, but that technique may not be sufficiently precise when, say, four to six or more materials are present in the same sample. For this and other reasons it has been widely believed by workers in the field that IR spectrometry was not generally capable of yielding valid quantitative results. 
     We have developed computer programs for use in the process to overcome the limitations of the prior art. With the programs, we first smooth the spectral curve obtained using a third-degree polynomial over an interval of five data points. The program then interrogates the smoothed curve in a twenty-one data point width, shifting one wave number at a time throughout the range of from 5000 wave numbers to 400 wave numbers. Spectral band profiles, positions and intensities are detected by comparing the fourth, fifth and sixth derivatives of the polynomial defining the curve. We have found that this technique yields the degree of precision necessary for the method to produce consistently valid quantitative results. 
     The efficacy of the present invention will be described further by reference to the following examples. In each example, the core sample was prepared in the lab so that the quantitative makeup of the sample was known. The sample was then analyzed according to the present invention and that result compared to the known sample makeup. 
    
    
     EXAMPLE I 
     A sample to be tested was prepared by mixing the following materials in the weight percent shown: 
     
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Mineral        Wt. Percent                                                
______________________________________                                    
Quartz         63.6                                                       
Calcite        15.2                                                       
Dolomite       15.7                                                       
Clay minerals  5.5                                                        
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     About 5 grams of the above core sample material was placed in a mortar and ground with a pestle until the largest particles were less than 0.5 millimeter in diameter. About 1 gram of the material was placed in a McCrone Micronising Mill to which about 5 milliliter of isopropyl alcohol were added. The material was ground for about 20 minutes which was sufficient to reduce the average particle size to less than 1 micron with no particles larger than 2 microns. The resultant sample liquid was poured off into a watch glass and placed under a vent hood for about 20 minutes, at which time the sample had dried to a powder. 1.67 milligrams of the powder was placed into a metal capsule to which about 1 gram of KBr was added and the capsule was shaken in a dental amalgamator for 1 minute. The capsule was placed in a 65° C. oven for about 10 minutes. 200.5 milligrams of the material in the capsule was then placed in a pellet press and pressed into 13 millimeter thin disk. The disk was placed in a Perkin-Elmer Model 1720 FTIR spectrometer, linked to a digital computer into which characteristic pure spectra had been stored in memory. The digital computer produced the following analysis observed for that single pellet so prepared: 
     
         ______________________________________                                    
Mineral        Weight Percent                                             
______________________________________                                    
Quartz         67.0                                                       
Calcite        14.0                                                       
Dolomite       16.0                                                       
Clay minerals  3.0                                                        
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     EXAMPLE II 
     The known sample was prepared as in Example I but having the makeup shown in the table below. The sample was then prepared for analysis in the same manner as described above, except that 1.56 milligrams of sample was combined with 1.015 grams of KBr and 201.2 milligrams of the mixture was used to produce the 13 millimeter pellet. The following results were obtained: 
     
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               Weight Percent                                             
Mineral          Actual  Observed                                         
______________________________________                                    
Quartz           13.4    13.0                                             
Plagioclase      49.9    51.0                                             
Microcline       15.2    17.0                                             
Calcite          15.7    12.0                                             
Clay minerals    5.5     7.0                                              
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     EXAMPLE III 
     The known sample was prepared as in Example I but having the makeup shown in the table below. The sample has then prepared for analysis in the same manner as described in Example I, except that 1.73 milligrams of sample was combined with 1.01 grams of KBr and 201.8 milligrams of the mixture was used to produce the 13 millimeter pellet. The following results were obtained: 
     
         ______________________________________                                    
               Weight Percent                                             
Mineral          Actual  Observed                                         
______________________________________                                    
Quartz           14.6    14.0                                             
Microcline       26.6    27.0                                             
Anhydrite        34.8    36.0                                             
Clay minerals    24.0    22.0                                             
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     EXAMPLE IV 
     The known sample was prepared as in Example I but having the makeup shown in the table below. The sample was then prepared for analysis in the same manner as described in Example I, except that 1.72 milligrams of sample was combined with 1.028 grams of KBr and 200.8 milligrams of the resulting mixture was used to produce the 13 millimeter pellet. The following results were obtained: 
     
         ______________________________________                                    
               Weight Percent                                             
Mineral          Actual  Observed                                         
Quartz           18.7    18.0                                             
Plagioclase      21.4    25.0                                             
Microcline       0.0     1.0                                              
Calcite          23.3    20.0                                             
Dolomite         32.5    33.0                                             
Clay minerals    4.1     3.0                                              
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     It can be seen that the results obtained using the method of the present invention in each case were within a few percent by weight of the known sample, and in each case produced accuracy acceptable for the geologic and lithologic analysis required in the oil and gas field. The time required in each case was limited to the total time involved in sample preparation, in all cases about 1 hour. 
     While the steps in the foregoing method have been described in considerable detail, it will be appreciated that such detail is provided for illustrative purposes and for completeness, and is not intended to limit the scope of the invention in any way, which invention is defined by the appended claims.