US20160195508A1 - Characterization of crude oil and its fractions by fluorescence spectroscopy analysis - Google Patents

Abstract

A system and a method are provided for calculating the cetane number, pour point, cloud point, aniline point, aromaticity, and/or octane number of a crude oil and its fractions from the density and fluorescence spectroscopy of a sample of the crude oil.

Description

CROSS-REFERENCE TO RELATED APPLICATION
• This application claims the benefit of U.S. Provisional Patent Application No. 62/099,703 filed Jan. 5, 2015, the disclosure of which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
• This invention relates to a method and process for the evaluation of samples of crude oil and its fractions by fluorescence spectroscopy analysis.
BACKGROUND OF THE INVENTION
• Crude oil originates from the decomposition and transformation of aquatic, mainly marine, living organisms and/or land plants that became buried under successive layers of mud and silt some 15-500 million years ago. They are essentially very complex mixtures of many thousands of different hydrocarbons. Depending on the source, the oil predominantly contains various proportions of straight and branched-chain paraffins, cycloparaffins, and naphthenic, aromatic, and polynuclear aromatic hydrocarbons. These hydrocarbons can be gaseous, liquid, or solid under normal conditions of temperature and pressure, depending on the number and arrangement of carbon atoms in the molecules.
• Crude oils vary widely in their physical and chemical properties from one geographical region to another and from field to field. Crude oils are usually classified into three groups according to the nature of the hydrocarbons they contain: paraffinic, naphthenic, asphaltic, and their mixtures. The differences are due to the different proportions of the various molecular types and sizes. One crude oil can contain mostly paraffins, another mostly naphthenes. Whether paraffinic or naphthenic, one can contain a large quantity of lighter hydrocarbons and be mobile or contain dissolved gases; another can consist mainly of heavier hydrocarbons and be highly viscous, with little or no dissolved gas. Crude oils can also include heteroatoms containing sulfur, nitrogen, nickel, vanadium and other elements in quantities that impact the refinery processing of the crude oil fractions. Light crude oils or condensates can contain sulfur in concentrations as low as 0.01 W %; in contrast, heavy crude oils can contain as much as 5-6 W %. Similarly, the nitrogen content of crude oils can range from 0.001-1.0 W %. The nature of the crude oil governs, to a certain extent, the nature of the products that can be manufactured from it and their suitability for special applications. A naphthenic crude oil will be more suitable for the production of asphaltic bitumen, a paraffinic crude oil for wax. A naphthenic crude oil, and even more so an aromatic one, will yield lubricating oils with viscosities that are sensitive to temperature. However, with modern refining methods there is greater flexibility in the use of various crude oils to produce many desired type of products.
• A crude oil assay is a traditional method of determining the nature of crude oils for benchmarking purposes. Crude oils are subjected to true boiling point (TBP) distillations and fractionations to provide different boiling point fractions. The crude oil distillations are carried out using the American Standard Testing Association (ASTM) Method D 2892. The common fractions and their nominal boiling points are given in Table 1.

• 	TABLE 1
  	Fraction	Boiling Point, ° C.
  	Methane	−161.5
  	Ethane	−88.6
  	Propane	−42.1
  	Butanes	−6.0
  	Light Naphtha	36-90
  	Mid Naphtha	90-160
  	Heavy Naphtha	160-205
  	Light gas Oil	205-260
  	Mid Gas Oil	260-315
  	Heavy gas Oil	315-370
  	Light Vacuum Gas Oil	370-430
  	Mid Vacuum Gas Oil	430-480
  	Heavy vacuum gas oil	480-565
  	Vacuum Residue	565+

• The yields, composition, physical and indicative properties of these crude oil fractions, where applicable, are then determined during the crude assay work-up calculations. Typical compositional and property information obtained from a crude oil assay is given in Table 2.

• TABLE 2
  Property	Unit	Property Type	Fraction
  Yield Weight and Volume %	W %	Yield	All
  API Gravity	°	Physical	All
  Viscosity Kinematic @ 38° C.	°	Physical	Fraction boiling >250° C.
  Refractive Index @ 20° C.	Unitless	Physical	Fraction boiling <400° C.
  Sulfur	W %	Composition	All
  Mercaptan Sulfur, W %	W %	Composition	Fraction boiling <250° C.
  Nickel	ppmw	Composition	Fraction boiling >400° C.
  Nitrogen	ppmw	Composition	All
  Flash Point, COC	° C.	Indicative	All
  Cloud Point	° C.	Indicative	Fraction boiling >250° C.
  Pour Point, (Upper)	° C.	Indicative	Fraction boiling >250° C.
  Freezing Point	° C.	Indicative	Fraction boiling >250° C.
  Micro Carbon Residue	W %	Indicative	Fraction boiling >300° C.
  Smoke Point, mm	mm	Indicative	Fraction boiling between
  			150-250° C.
  Octane Number	Unitless	Indicative	Fraction boiling <250° C.
  Cetane Index	Unitless	Indicative	Fraction boiling between
  			150-400° C.
  Aniline Point	° C.	Indicative	Fraction boiling <520° C.

• Due to the number of distillation cuts and the number of analyses involved, the crude oil assay work-up is both costly and time consuming.
• In a typical refinery, crude oil is first fractionated in the atmospheric distillation column to separate sour gas and light hydrocarbons, including methane, ethane, propane, butanes and hydrogen sulfide, naphtha (36-180° C.), kerosene (180-240° C.), gas oil (240-370° C.) and atmospheric residue (>370° C.). The atmospheric residue from the atmospheric distillation column is either used as fuel oil or sent to a vacuum distillation unit, depending on the configuration of the refinery. The principal products obtained from vacuum distillation are vacuum gas oil, comprising hydrocarbons boiling in the range 370-520° C., and vacuum residue, comprising hydrocarbons boiling above 520° C. Crude assay data is conventionally obtained from individual analysis of these cuts to help refiners to understand the general composition of the crude oil fractions and properties so that the fractions can be processed most efficiently and effectively in an appropriate refining unit. Indicative properties are used to determine the engine/fuel performance or usability or flow characteristic or composition. A summary of the indicative properties and their determination methods with description is given below.
• The cetane number of diesel fuel oil, determined by the ASTM D613 method, provides a measure of the ignition quality of diesel fuel; as determined in a standard single cylinder test engine; which measures ignition delay compared to primary reference fuels. The higher the cetane number; the easier the high-speed; direct-injection engine will start; and the less white smoking and diesel knock after start-up are. The cetane number of a diesel fuel oil is determined by comparing its combustion characteristics in a test engine with those for blends of reference fuels of known cetane number under standard operating conditions. This is accomplished using the bracketing hand wheel procedure which varies the compression ratio (hand wheel reading) for the sample and each of the two bracketing reference fuels to obtain a specific ignition delay, thus permitting interpolation of cetane number in terms of hand wheel reading.
• The cloud point, determined by the ASTM D2500 method, is the temperature at which a cloud of wax crystals appears when a lubricant or distillate fuel is cooled under standard conditions. Cloud point indicates the tendency of the material to plug filters or small orifices under cold weather conditions. The specimen is cooled at a specified rate and examined periodically. The temperature at which cloud is first observed at the bottom of the test jar is recorded as the cloud point. This test method covers only petroleum products and biodiesel fuels that are transparent in 40 mm thick layers, and with a cloud point below 49° C.
• The pour point of petroleum products, determined by the ASTM D97 method, is an indicator of the ability of oil or distillate fuel to flow at cold operating temperatures. It is the lowest temperature at which the fluid will flow when cooled under prescribed conditions. After preliminary heating, the sample is cooled at a specified rate and examined at intervals of 3° C. for flow characteristics. The lowest temperature at which movement of the specimen is observed is recorded as the pour point.
• The aniline point, determined by the ASTM D611 method, is the lowest temperature at which equal volumes of aniline and hydrocarbon fuel or lubricant base stock are completely miscible. A measure of the aromatic content of a hydrocarbon blend is used to predict the solvency of a base stock or the cetane number of a distillate fuel. Specified volumes of aniline and sample, or aniline and sample plus n-heptane, are placed in a tube and mixed mechanically. The mixture is heated at a controlled rate until the two phases become miscible. The mixture is then cooled at a controlled rate and the temperature at which two separate phases are again formed is recorded as the aniline point or mixed aniline point.
• The octane number, determined by the ASTM D2699 or D2700 methods, is a measure of a fuel's ability to prevent detonation in a spark ignition engine. Measured in a standard single-cylinder; variable-compression-ratio engine by comparison with primary reference fuels. Under mild conditions, the engine measures research octane number (RON), while under severe conditions, the engine measures motor octane number (MON). Where the law requires posting of octane numbers on dispensing pumps, the antiknock index (AKI) is used. This is the arithmetic average of RON and MON, (R+M)/2. It approximates the road octane number, which is a measure of how an average car responds to the fuel.
• To determine these properties of gas oil or naphtha fractions conventionally, these fractions have to be distilled from the crude oil and then measured/identified using various analytical methods that are laborious, costly and time-consuming.
• Fluorescence spectrometry is a sensitive and selective analytical method for aromatic-containing samples like crude oil. Therefore, it is particularly useful for the determination of condensed aromatic or heteroaromatic ring compounds in crude oil. Fluorescence occurs when a fluorescent material is excited by absorbing an incident light (photon) into a higher electronic state which will return to the ground state after emitting light (a photon) from the ground vibrational level of the excited electronic state. The emitted photon goes to an excited vibrational state of the ground electronic state. The structure and environments of the fluorescent material can be deduced from the energies and relative intensities of the fluorescence signals.
• A fluorescence emission spectrum is recorded when the excitation wavelength of light is held constant and the emission beam is scanned as a function of wavelength. An excitation spectrum is the opposite, whereby the emission light is held at a constant wavelength, and the excitation light is scanned as a function of wavelength. The excitation spectrum usually resembles the absorbance spectrum in shape.
• Synchronous fluorescence spectrometry is the method of choice to improve the selectivity of the measurement by taking full advantage of the ability to vary both the excitation and the emission wavelength during analysis. Excitation and emission wavelengths are scanned simultaneously while maintaining a constant wavelength difference between the two modes. This method has been proved successful for materials like polycyclic aromatic hydrocarbons.
• This invention discloses a system and method in which fluorescence spectroscopy analysis is employed to disclose physical and indicative properties (i.e., cetane number, pour point, cloud point, and aniline point) of gas oil fraction of crude oils, as well as the octane number of the naphtha fraction and the aromaticity of whole crude oils. The invention provides insight into the gas oil properties without fractionation/distillation (crude oil assays) and will help producers, refiners, and marketers to benchmark the oil quality and, as a result, valuate the oils without going thru costly and time consuming crude oil assays. Whereas a conventional crude oil assay method could take up to two months, this invention provides results within one hour.
• New rapid, and direct methods to help better understand crude oil compositions and properties from analysis of whole crude oil will save producers, marketers, refiners and/or other crude oil users substantial expense, effort and time. Therefore, a need exists for an improved system and method for determining indicative properties of crude oil fractions from different sources.
SUMMARY OF THE INVENTION
• Systems and methods for determining one or more indicative properties of a hydrocarbon sample are presented. Indicative properties in a crude oil sample (e.g., cetane number, pour point, cloud point and aniline point) of a gas oil fraction, octane number of a naphtha fraction, and the aromaticity for the whole crude oil (WCO), are assigned as a function of density and fluorescence spectroscopy measurement of a crude oil sample. The indicative properties provide information about the gas oil and naphtha properties without fractionation/distillation (crude oil assays) and help producers, refiners, and marketers to benchmark the oil quality and, as a result, valuate the oils without performing the customary extensive and time-consuming crude oil assays.
BRIEF DESCRIPTION OF THE DRAWINGS
• Further advantages and features of the present invention will become apparent from the following detailed description of the invention when considered with reference to the accompanying drawings in which:
• FIG. 1 is a graphic plot of typical fluorescence spectroscopy data for typical crude oil samples with different API gravities;
• FIG. 2 is a block diagram of a method in which an embodiment of the invention is implemented;
• FIG. 3 is a schematic block diagram of modules of an embodiment of the invention; and
• FIG. 4 is a block diagram of a computer system in which an embodiment of the invention is implemented.
DETAILED DESCRIPTION OF INVENTION
• A system and a method are provided for determining one or more indicative properties of a hydrocarbon sample. Indicative properties (e.g., cetane number, pour point, cloud point, and aniline point) of a gas oil fraction and ozone number of a naphtha fraction in a crude oil sample are assigned as a function of the density and fluorescence spectroscopy measurement of the crude oil sample. The indicative properties provide information about the gas oil and naphtha properties without fractionation/distillation (crude oil assays) and help producers, refiners, and marketers to benchmark the oil quality and, as a result, valuate the oils without performing the customary extensive and time-consuming crude oil assays.
• The systems and methods are applicable for naturally occurring hydrocarbons derived from crude oils, bitumens, heavy oils, shale oils and from refinery process units including hydrotreating, hydroprocessing, fluid catalytic cracking, coking, and visbreaking or coal liquefaction.
• In the system and method herein, fluorescence spectroscopy analysis is obtained by a suitable known or to-be-developed process. Fluorescence spectroscopy uses a fluorometer to collect spectral data of a solid, liquid, or gas.
• In one embodiment, a Varian Cary Eclipse fluorescence spectrophotometer (i.e., fluorometer) was used for the analysis of the crude oil. The synchronization scanning mode was utilized, with a delta of 15 nm, and a scan range from 250-800 nm.
• Typical fluorescence spectroscopy data for crude oils with different API gravities is shown in FIG. 1.
• In one embodiment, the fluorescence spectroscopy index is calculated as follows. The absorbance unit at each wavelength (integer) of the scan range is summed, and then the total is divided by 1000.
• $\begin{array}{cc}{\mathrm{FSMI}}_{\mathrm{crude\_oil}}=\sum _{f=250}^{800}\left(\mathrm{Absorbance}\mathrm{Unit}\right)/\left(1000\right)& \left(1\right)\end{array}$
• FIG. 2 shows a process flowchart of steps in a method according to one embodiment herein, in which crude oil samples are prepared and analyzed by fluorescence spectroscopy according to the method 200 described below.
• In step 210 a sample of crude oil is dissolved in hexane and then scanned by the fluorometer over the wavelength range from 250-800 nm.
• In step 215, the fluorescence spectroscopy data is arranged by wavelength and absorbance unit.
• In step 220, a fluorescence spectroscopy index is calculated according to equation (1).
• The indicative properties (e.g., the cetane number, pour point, cloud point and aniline point) of the gas oil fraction, e.g. boiling in the range of 150-400° C. and in certain embodiments in the range of 180-370° C., the octane number of the naphtha fraction, and the aromaticity for the whole crude oil (WCO), can be assigned as a function of the density and the fluorescence spectroscopy index of crude oil. That is,
• 
  Indicative Property=f(density_{crude oil} ,FSMI _crudeoil)  (2);
• Equation (3) is a detailed example of this relationship, showing the cetane number, pour point, cloud point and aniline point that can be predicted for the gas oil (GO) fraction of the crude oil, as well as the aromaticity that can be predicted for the whole crude oil (WCO), as well as the octane number that can be predicted for the naphtha fraction.
• In steps 235, 240, 245, and 250, respectively, the properties of a cetane number, pour point, cloud point and aniline point for the gas oil (GO) fraction of the crude oil are calculated, in step 253 the aromaticity for the whole crude oil (WCO) is calculated, and in step 255 the property of an octane number for the naphtha fraction of the crude oil is calculated. While FIG. 2 shows the steps performed sequentially, they can be performed in parallel or in any order. In certain embodiments, only one or more steps 235, 240, 245, 250, 253, 255 are carried out. In these steps, the one or more indicative properties are determined as follows:
• 
  Indicative property=K+X1*DEN+X2*DEN² +X3*DEN³ +X4*FSMI+X5*FSMI ² +X6*FSMI ³ +X7*DEN*FSMI  (3);
• where:
• DEN=density of the crude oil sample; and
• K, X1-X7, are constants for the properties to be predicted that are developed using linear regression analysis of hydrocarbon data from fluorescence spectrometry data.
• FIG. 3 illustrates a schematic block diagram of modules in accordance with an embodiment of the present invention, system 300. Density and raw data receiving module 310 receives the density of a sample of crude oil and fluorescence spectroscopy data derived from the crude oil.
• Fluorescence spectroscopy index calculation module 315 calculates the fluorescence spectroscopy index from the spectral data.
• Cetane number calculation module 335 derives the cetane number for the gas oil fraction of the crude oil as a function of the fluorescence spectroscopy index and density of the sample.
• Pour point calculation module 340 derives the pour point for the gas oil fraction of the crude oil as a function of the fluorescence spectroscopy index and density of the sample.
• Cloud point calculation module 345 derives the cloud point for the gas oil fraction of the crude oil as a function of the fluorescence spectroscopy index and density of the sample.
• Aniline point calculation module 350 derives the aniline point for the gas oil fraction of the crude oil as a function of the fluorescence spectroscopy index and density of the sample.
• Aromaticity calculation module 352 derives the aromaticity for the whole crude oil as a function of the fluorescence spectroscopy index and density of the sample.
• Octane number calculation module 355 derives the octane number for the naphtha fraction of the crude oil as a function of the fluorescence spectroscopy index and density of the sample.
• FIG. 4 shows an exemplary block diagram of a computer system 400 in which one embodiment of the present invention can be implemented. Computer system 400 includes a processor 420, such as a central processing unit, an input/output interface 430 and support circuitry 440. In certain embodiments, where the computer system 400 requires a direct human interface, a display 410 and an input device 450 such as a keyboard, mouse or pointer are also provided. The display 410, input device 450, processor 420, and support circuitry 440 are shown connected to a bus 490 which also connects to a memory 460. Memory 460 includes program storage memory 470 and data storage memory 480. Note that while computer system 400 is depicted with direct human interface components display 410 and input device 450, programming of modules and exportation of data can alternatively be accomplished over the input/output interface 430, for instance, where the computer system 400 is connected to a network and the programming and display operations occur on another associated computer, or via a detachable input device as is known with respect to interfacing programmable logic controllers.
• Program storage memory 470 and data storage memory 480 can each comprise volatile (RAM) and non-volatile (ROM) memory units and can also comprise hard disk and backup storage capacity, and both program storage memory 470 and data storage memory 480 can be embodied in a single memory device or separated in plural memory devices. Program storage memory 470 stores software program modules and associated data, and in particular stores a density and raw data receiving module 310, fluorescence spectroscopy index calculation module 315, cetane number calculation module 335, pour point calculation module 340, cloud point calculation module 345, aniline point calculation module 350, aromaticity calculation module 352, and octane number calculation module 355. Data storage memory 480 stores results and other data generated by the one or more modules of the present invention.
• It is to be appreciated that the computer system 400 can be any computer such as a personal computer, minicomputer, workstation, mainframe, a dedicated controller such as a programmable logic controller, or a combination thereof. While the computer system 400 is shown, for illustration purposes, as a single computer unit, the system can comprise a group of computers which can be scaled depending on the processing load and database size.
• Computer system 400 preferably supports an operating system, for example stored in program storage memory 470 and executed by the processor 420 from volatile memory. According to an embodiment of the invention, the operating system contains instructions for interfacing computer system 400 to the Internet and/or to private networks.
Example 1
• A set of constants K and X1-X7 was determined using linear regression for the indicative properties cetane number, pour point, cloud point, aniline point, octane number, and aromaticity. These constants were determined based on known actual distillation data for plural crude oil samples and their corresponding indicative properties. These constants are given in Table 3.

• TABLE 3
  Constants	Cetane Number	Pour Point	Cloud Point
  K	−2.920657E+04	−2.283807E+04	8.016178E+04
  X1	8.247657E+04	6.995129E+04	−2.781445E+05
  X2	−8.008823E+04	−7.232753E+04	3.199487E+05
  X3	2.758504E+04	2.532512E+04	−1.219746E+05
  X4	1.273387E+02	4.791017E+01	3.108188E+01
  X5	4.207752E−01	−8.303909E−02	1.963374E−01
  X6	−4.676128E−03	7.142002E−04	−1.983566E−03
  X7	−1.581570E+02	−5.156225E+01	−4.212763E+01
  Constants	Aniline Point	Octane Number	WCO-AROM
  K	−4.370054E+04	1.017323E+05	1.047903E+04
  X1	1.449824E+05	−3.438191E+05	−4.741776E+04
  X2	−1.608909E+05	3.877252E+05	6.274074E+04
  X3	5.979962E+04	−1.457003E+05	−2.516125E+04
  X4	2.649713E+01	−9.217455E+00	8.586987E+01
  X5	−5.686953E−02	2.914821E−01	6.843602E−01
  X6	3.346494E−04	−2.737219E−03	−7.078907E−03
  X7	−2.749938E+01	0.000000E+00	−1.207479E+02

• The following example is provided to demonstrate an application of equations (3). A sample of Arabian medium crude with a 15° C./4° C. density of 0.8828 Kg/1 was analyzed by fluorescence spectroscopy, using the described method. The tabulated results follow in Table 4:

• 	TABLE 4
  	API Gravity, °

  Wavelength (nm)	28.8	19.6

  250	1.27	1.05
  251	1.21	0.91
  252	1.14	0.85
  253	0.95	1.02
  254	0.97	0.92
  255	1.15	0.94
  256	1.28	1.09
  257	1.33	1.44
  258	1.57	1.44
  259	1.83	1.63
  260	2.05	1.96
  261	2.63	2.21
  262	3.16	2.73
  263	3.74	3.25
  264	4.28	3.88
  265	5.00	5.07
  266	5.67	5.59
  267	6.48	6.78
  268	6.65	7.27
  269	7.56	8.55
  270	7.85	9.29
  271	8.36	9.87
  272	8.71	10.68
  273	8.93	11.21
  274	9.24	11.49
  275	8.79	12.13
  276	8.60	12.45
  277	8.79	12.68
  278	8.35	12.72
  279	7.74	12.31
  280	7.50	12.34
  281	7.35	12.60
  282	7.42	12.55
  283	7.79	13.13
  284	9.11	14.59
  285	10.15	16.48
  286	12.32	19.70
  287	14.84	23.30
  288	17.17	27.11
  289	20.36	31.74
  290	22.93	36.59
  291	24.17	40.13
  292	26.52	44.18
  293	28.00	46.89
  294	27.89	49.52
  295	28.54	51.24
  296	29.29	54.14
  297	30.29	56.46
  298	30.41	58.06
  299	31.50	60.48
  300	31.99	62.98
  301	32.14	63.77
  302	32.38	66.72
  303	31.66	66.79
  304	31.23	67.48
  305	29.79	66.10
  306	28.95	65.39
  307	27.11	64.41
  308	26.08	63.97
  309	25.76	62.65
  310	25.31	62.52
  311	24.73	62.68
  312	25.28	64.40
  313	26.44	67.67
  314	27.19	69.71
  315	27.25	68.99
  316	28.15	70.95
  317	29.82	73.39
  318	31.36	78.28
  319	32.10	81.73
  320	34.13	85.19
  321	34.44	87.23
  322	37.79	94.02
  323	40.61	101.62
  324	43.34	109.60
  325	46.36	117.56
  326	47.79	124.76
  327	51.11	134.00
  328	54.09	143.32
  329	56.67	152.26
  330	58.77	159.16
  331	58.02	159.37
  332	60.10	165.95
  333	61.49	168.93
  334	63.50	176.30
  335	63.66	172.61
  336	63.59	173.20
  337	62.73	175.41
  338	65.47	181.41
  339	68.17	184.71
  340	69.14	188.76
  341	68.81	184.04
  342	70.78	187.74
  343	71.17	186.11
  344	74.48	194.29
  345	74.95	192.86
  346	75.31	196.13
  347	76.25	191.86
  348	76.99	192.92
  349	77.96	192.59
  350	80.27	194.30
  351	78.27	190.40
  352	77.50	188.90
  353	77.98	184.87
  354	78.21	187.44
  355	78.16	185.91
  356	78.36	184.15
  357	76.17	178.69
  358	76.24	175.44
  359	75.49	174.06
  360	76.48	175.46
  361	75.71	173.24
  362	77.62	172.86
  363	77.05	169.22
  364	78.20	171.83
  365	77.52	167.50
  366	79.23	167.43
  367	77.33	161.66
  368	78.10	161.76
  369	76.25	156.31
  370	77.04	153.14
  371	75.00	151.36
  372	76.69	151.51
  373	76.13	148.03
  374	75.95	147.92
  375	74.56	146.40
  376	77.28	153.98
  377	78.71	157.11
  378	80.95	165.33
  379	81.67	167.60
  380	83.41	174.64
  381	86.26	181.18
  382	87.37	189.91
  383	88.30	194.12
  384	90.10	196.70
  385	89.27	199.14
  386	91.91	204.95
  387	92.77	210.50
  388	91.22	210.57
  389	91.49	210.34
  390	90.72	211.38
  391	90.54	209.72
  392	91.19	213.29
  393	92.41	216.90
  394	92.39	218.13
  395	93.00	220.83
  396	93.93	220.46
  397	94.01	222.20
  398	93.90	222.32
  399	93.41	223.02
  400	92.18	221.82
  401	91.00	220.53
  402	91.43	219.05
  403	91.29	218.84
  404	92.06	218.51
  405	91.49	219.09
  406	92.58	218.48
  407	91.94	216.00
  408	91.44	216.14
  409	92.37	215.76
  410	91.80	212.67
  411	90.76	210.61
  412	89.27	209.16
  413	89.74	205.68
  414	89.07	203.71
  415	88.22	200.33
  416	87.09	198.86
  417	87.18	197.27
  418	86.86	195.36
  419	86.88	195.24
  420	87.05	195.64
  421	87.44	195.13
  422	87.04	194.82
  423	87.33	192.77
  424	87.21	192.40
  425	87.65	191.73
  426	87.08	191.12
  427	87.11	189.04
  428	85.32	187.05
  429	85.49	184.34
  430	83.64	180.80
  431	83.72	177.67
  432	83.13	178.84
  433	83.41	177.03
  434	83.70	175.80
  435	82.78	175.25
  436	81.67	173.03
  437	81.69	172.99
  438	81.69	170.94
  439	81.37	170.17
  440	81.09	169.31
  441	80.69	169.08
  442	79.95	167.44
  443	79.43	165.50
  444	78.64	163.07
  445	78.29	161.13
  446	78.06	160.86
  447	77.39	159.34
  448	76.72	158.48
  449	76.97	157.38
  450	76.05	154.39
  451	74.74	153.40
  452	74.13	151.33
  453	73.35	148.34
  454	72.50	146.80
  455	71.39	144.42
  456	70.29	140.20
  457	69.49	139.33
  458	67.91	136.19
  459	67.47	136.30
  460	66.83	134.80
  461	66.13	133.01
  462	65.91	132.51
  463	64.99	129.55
  464	64.42	127.25
  465	62.81	125.11
  466	61.35	121.38
  467	60.41	119.99
  468	59.29	118.29
  469	59.48	116.76
  470	57.97	114.85
  471	57.34	113.47
  472	56.76	112.23
  473	54.83	109.40
  474	54.62	107.56
  475	53.24	105.06
  476	52.40	103.80
  477	51.24	102.89
  478	50.54	100.46
  479	49.71	98.76
  480	48.71	95.76
  481	46.65	91.87
  482	46.75	92.08
  483	45.58	91.72
  484	45.47	90.16
  485	44.77	90.37
  486	44.22	89.52
  487	44.13	88.40
  488	42.93	87.33
  489	41.99	85.13
  490	41.09	83.09
  491	40.30	81.43
  492	39.87	81.19
  493	39.07	79.56
  494	38.61	78.01
  495	37.54	76.65
  496	36.22	75.01
  497	35.59	73.99
  498	35.13	71.41
  499	34.20	71.86
  500	34.18	70.05
  501	32.85	69.17
  502	31.72	67.31
  503	31.47	66.49
  504	30.76	64.14
  505	30.20	63.20
  506	29.32	62.69
  507	29.02	61.29
  508	27.78	59.76
  509	27.66	58.69
  510	27.14	58.04
  511	27.02	56.90
  512	26.38	56.02
  513	25.72	55.28
  514	25.03	53.66
  515	24.12	52.39
  516	24.26	51.68
  517	23.67	50.34
  518	22.48	49.83
  519	22.56	48.20
  520	22.12	48.16
  521	21.43	46.61
  522	20.92	45.44
  523	20.12	44.67
  524	19.80	43.49
  525	19.30	41.61
  526	18.87	41.21
  527	18.46	40.69
  528	18.36	40.39
  529	18.06	39.71
  530	17.67	39.44
  531	17.75	38.55
  532	16.95	37.58
  533	16.58	36.48
  534	16.11	35.58
  535	15.88	35.02
  536	15.72	34.58
  537	15.33	33.95
  538	14.77	32.36
  539	14.15	31.44
  540	13.74	31.22
  541	13.51	30.52
  542	13.34	30.13
  543	13.22	29.26
  544	13.03	29.66
  545	12.49	28.66
  546	12.34	28.03
  547	11.71	27.70
  548	11.95	27.46
  549	11.78	27.10
  550	11.40	26.31
  551	11.10	25.65
  552	10.85	25.14
  553	10.40	24.94
  554	10.11	24.16
  555	10.30	23.22
  556	10.01	23.19
  557	9.85	22.60
  558	8.94	22.71
  559	9.08	22.36
  560	9.14	21.25
  561	8.91	20.57
  562	8.48	20.23
  563	8.41	19.76
  564	8.33	18.95
  565	8.13	19.24
  566	7.50	18.61
  567	7.78	17.66
  568	7.69	17.33
  569	7.45	17.61
  570	7.12	17.31
  571	6.95	17.03
  572	6.82	16.17
  573	6.63	16.20
  574	6.43	15.86
  575	6.71	15.62
  576	6.40	15.06
  577	6.37	14.35
  578	6.13	14.40
  579	6.28	14.51
  580	6.08	13.72
  581	5.51	13.78
  582	5.54	13.23
  583	5.53	13.24
  584	5.29	13.22
  585	5.72	12.35
  586	5.00	12.14
  587	4.98	12.07
  588	4.82	11.48
  589	4.81	12.04
  590	4.79	11.35
  591	4.52	11.28
  592	4.46	10.10
  593	4.32	10.52
  594	4.28	10.09
  595	3.88	9.88
  596	4.10	9.57
  597	4.18	9.47
  598	3.96	9.79
  599	3.80	9.14
  600	3.78	8.88
  601	3.67	8.30
  602	3.43	8.49
  603	3.49	7.82
  604	3.28	7.81
  605	3.13	7.45
  606	3.02	7.76
  607	3.29	7.62
  608	3.43	7.53
  609	2.84	7.36
  610	2.95	7.37
  611	2.87	6.67
  612	2.72	6.99
  613	2.64	6.74
  614	2.52	6.59
  615	2.52	6.29
  616	2.60	6.30
  617	2.56	6.07
  618	2.24	5.60
  619	2.74	5.61
  620	2.47	5.92
  621	2.19	5.51
  622	2.03	5.41
  623	2.37	5.22
  624	2.09	5.13
  625	1.75	5.14
  626	1.71	4.92
  627	2.15	5.04
  628	1.93	5.05
  629	1.72	4.74
  630	2.01	4.89
  631	1.66	4.58
  632	1.95	4.53
  633	1.55	4.44
  634	2.03	4.36
  635	1.58	4.14
  636	2.00	3.74
  637	1.52	3.30
  638	1.32	3.85
  639	1.23	3.82
  640	1.77	4.04
  641	1.55	3.56
  642	1.67	3.38
  643	1.22	4.22
  644	0.91	3.78
  645	1.64	3.38
  646	1.23	3.97
  647	1.51	3.16
  648	1.53	3.30
  649	1.41	3.55
  650	1.29	2.64
  651	1.47	3.08
  652	1.35	2.82
  653	1.22	2.66
  654	1.13	3.13
  655	1.33	2.87
  656	1.26	3.11
  657	1.08	2.09
  658	1.33	2.52
  659	0.98	2.46
  660	1.11	2.75
  661	1.19	2.34
  662	1.06	2.20
  663	1.07	2.86
  664	1.08	2.43
  665	1.10	2.58
  666	1.22	2.34
  667	0.94	2.20
  668	1.20	2.27
  669	0.71	2.07
  670	1.31	1.99
  671	0.43	2.20
  672	0.81	1.48
  673	0.84	1.90
  674	0.91	2.07
  675	0.39	1.79
  676	0.82	2.07
  677	1.05	1.47
  678	1.13	2.14
  679	1.20	1.85
  680	0.68	1.99
  681	0.81	1.50
  682	0.30	1.87
  683	1.03	1.52
  684	1.03	2.16
  685	0.50	1.90
  686	1.02	1.91
  687	0.67	1.58
  688	0.65	1.51
  689	0.51	1.43
  690	0.44	0.97
  691	0.79	1.73
  692	0.93	1.19
  693	0.94	1.40
  694	0.84	1.35
  695	0.66	1.36
  696	0.99	1.20
  697	0.73	0.89
  698	0.48	1.71
  699	0.68	1.29
  700	0.43	1.74
  701	0.58	1.96
  702	0.70	1.07
  703	0.78	1.19
  704	0.69	1.35
  705	0.95	1.17
  706	−0.49	1.69
  707	1.10	1.38
  708	0.68	1.76
  709	0.61	1.09
  710	0.71	0.90
  711	0.54	1.03
  712	0.09	1.59
  713	0.18	1.59
  714	1.18	0.75
  715	0.83	0.84
  716	0.28	1.45
  717	0.39	1.22
  718	0.51	0.53
  719	−0.22	1.01
  720	0.36	1.35
  721	0.37	0.90
  722	0.00	0.13
  723	0.65	1.08
  724	0.93	1.09
  725	1.22	0.70
  726	1.08	0.28
  727	−0.67	0.84
  728	0.40	0.56
  729	0.40	1.81
  730	1.33	0.14
  731	−0.13	1.12
  732	0.81	0.84
  733	−0.83	1.29
  734	−0.28	1.63
  735	0.60	0.47
  736	−0.63	0.81
  737	0.16	0.34
  738	0.68	1.58
  739	0.35	2.00
  740	−0.90	1.68
  741	0.37	1.34
  742	0.00	−0.99
  743	−0.59	0.40
  744	0.20	1.04
  745	0.60	2.53
  746	−1.04	1.07
  747	−0.62	1.32
  748	−0.42	1.54
  749	−0.21	0.00
  750	−0.42	0.66
  751	1.30	0.46
  752	0.87	−0.23
  753	0.00	0.46
  754	0.22	0.70
  755	−0.46	0.48
  756	1.63	1.23
  757	0.00	2.24
  758	0.24	−0.25
  759	0.00	0.75
  760	1.92	−1.02
  761	−0.24	2.00
  762	−0.47	2.65
  763	2.18	1.61
  764	0.43	0.67
  765	0.87	−0.45
  766	0.45	0.95
  767	−0.24	1.52
  768	0.00	1.90
  769	0.55	−0.28
  770	−0.58	0.30
  771	−0.90	0.62
  772	0.31	1.27
  773	1.57	0.97
  774	0.96	0.34
  775	−0.64	0.34
  776	0.65	−1.03
  777	0.32	−1.72
  778	−1.64	−0.69
  779	−0.68	1.75
  780	0.34	1.73
  781	−1.71	0.00
  782	0.35	3.25
  783	0.00	0.36
  784	0.00	0.73
  785	2.13	−1.12
  786	1.43	0.74
  787	1.06	0.00
  788	0.70	0.00
  789	2.76	0.73
  790	1.41	3.24
  791	1.05	−0.37
  792	−0.36	0.00
  793	−0.71	2.27
  794	−1.46	3.03
  795	0.73	1.12
  796	−0.36	0.74
  797	0.37	−1.11
  798	−1.08	0.74
  799	1.09	1.14
  800	−0.37	1.88

• The spectrum obtained from fluorescence spectroscopy is wavelength vs. absorption unit. The FSMI is then calculated by taking the sum of each absorbance unit at each wavelength (integer) and then dividing by 1000.
• Applying equation (1), FSMI for the oil “AM” under investigation was calculated to be 15.639. The FSMI for all of the oils shown in FIG. 1 was similarly calculated, and is shown in Table 5, below.

• 	TABLE 5
  	AM	AH	L1	SSL	XSL	UR	BI	IHI	MB

  API	28.8	27.4	30.3	30.2	36.8	31.6	30.8	30.0	19.6
  Gravity, °
  FSMI	15.639	32.086	38.436	11.951	37.938	50.243	38.549	42.667	34.691

• Applying equation (3) and the constants from Table 3, for the oil “AM” under review:
• $\mathrm{Cetane}{\mathrm{Number}}_{\mathrm{GO}}\left(\mathrm{CET}\right)=K_{\mathrm{CET}}+X1_{\mathrm{CET}}*\mathrm{DEN}+X2_{\mathrm{CET}}*{\mathrm{DEN}}^2+X3_{\mathrm{CET}}*{\mathrm{DEN}}^3+X4_{\mathrm{CET}}*\mathrm{FSMI}+X5_{\mathrm{CET}}*{\mathrm{FSMI}}^2+X6_{\mathrm{CET}}*{\mathrm{FSMI}}^3+X7_{\mathrm{CET}}*\mathrm{DEN}*\mathrm{FSMI}=\left(-2.920657E+04\right)+\left(8.247657E+04\right)\left(0.8828\right)+\left(-8.008823E+04\right){\left(0.8828\right)}^2+\left(2.758504E+04\right){\left(0.8828\right)}^3+\left(1.273387E+02\right)\left(15.369\right)+\left(4.207752E-01\right){\left(15.369\right)}^2+\left(-4.676128E-03\right){\left(15.369\right)}^3+\left(-1.581570E+02\right)\left(0.8828\right)\left(15.369\right)=59$ $\mathrm{Pour}{\mathrm{Point}}_{\mathrm{GO}}\left(\mathrm{PP}\right)=K_{\mathrm{PP}}+X1_{\mathrm{PP}}*\mathrm{DEN}+X2_{\mathrm{PP}}*{\mathrm{DEN}}^2+X3_{\mathrm{PP}}*{\mathrm{DEN}}^3+X4_{\mathrm{PP}}*\mathrm{FSMI}+X5_{\mathrm{PP}}*{\mathrm{FSMI}}^2+X6_{\mathrm{PP}}*{\mathrm{FSMI}}^3+X7_{\mathrm{PP}}*\mathrm{DEN}*\mathrm{FSMI}=\left(-2.283807E+04\right)+\left(6.995129E+04\right)\left(0.8828\right)+\left(-7.232753E+04\right){\left(0.8828\right)}^2+\left(2.532512E+04\right){\left(0.8828\right)}^3+\left(4.791017E+01\right)\left(15.369\right)+\left(-8.303909E-02\right){\left(15.369\right)}^2+\left(7.142002E-04\right){\left(15.369\right)}^3+\left(-5.156225E+01\right)\left(0.8828\right)\left(15.369\right)=-10$ $\mathrm{Cloud}{\mathrm{Point}}_{\mathrm{GO}}\left(\mathrm{CP}\right)=K_{\mathrm{CP}}+X1_{\mathrm{CP}}*\mathrm{DEN}+X2_{\mathrm{CP}}*{\mathrm{DEN}}^2+X3_{\mathrm{CP}}*{\mathrm{DEN}}^3+X4_{\mathrm{CP}}*\mathrm{FSMI}+X5_{\mathrm{CP}}*{\mathrm{FSMI}}^2+X6_{\mathrm{CP}}*{\mathrm{FSMI}}^3+X7_{\mathrm{CP}}*\mathrm{DEN}*\mathrm{FSMI}=\left(8.016178E+04\right)+\left(-2.781445E+05\right)\left(0.8828\right)+\left(3.199487E+05\right){\left(0.8828\right)}^2+\left(-1.219746E+05\right){\left(0.8828\right)}^3+\left(3.108188E+01\right)\left(15.369\right)+\left(1.963374E-01\right){\left(15.369\right)}^2+\left(-1.983566E-03\right){\left(15.369\right)}^3+\left(-4.212763E+01\right)\left(0.8828\right)\left(15.369\right)=-10$ $\mathrm{Aniline}{\mathrm{Point}}_{\mathrm{GO}}\left(\mathrm{AP}\right)=K_{\mathrm{AP}}+X1_{\mathrm{AP}}*\mathrm{DEN}+X2_{\mathrm{AP}}*{\mathrm{DEN}}^2+X3_{\mathrm{AP}}*{\mathrm{DEN}}^3+X4_{\mathrm{AP}}*\mathrm{FSMI}+X5_{\mathrm{AP}}*{\mathrm{FSMI}}^2+X6_{\mathrm{AP}}*{\mathrm{FSMI}}^3+X7_{\mathrm{AP}}*\mathrm{DEN}*\mathrm{FSMI}=\left(-4.370054E+04\right)+\left(1.44982E+05\right)\left(0.8828\right)+\left(-1.608909E+05\right){\left(0.8828\right)}^2+\left(5.979962E+04\right){\left(0.8828\right)}^3+\left(2.649713E+01\right)\left(15.369\right)+\left(-5.686953E-02\right){\left(15.369\right)}^2+\left(3.346494E-04\right){\left(15.369\right)}^3+\left(-2.749938E+01\right)\left(0.8828\right)\left(15.369\right)=66$ ${\mathrm{Aromaticity}}_{\mathrm{WCO}}\left(\mathrm{AROM}\right)=K_{\mathrm{AROM}}+X1_{\mathrm{AROM}}*\mathrm{DEN}+X2_{\mathrm{AROM}}*{\mathrm{DEN}}^2+X3_{\mathrm{AROM}}*{\mathrm{DEN}}^3+X4_{\mathrm{AROM}}*\mathrm{FSMI}+X5_{\mathrm{AROM}}*{\mathrm{FSMI}}^2+X6_{\mathrm{AROM}}*{\mathrm{FSMI}}^3+X7_{\mathrm{AROM}}*\mathrm{DEN}*\mathrm{FSMI}=\left(1.047903E+04\right)+\left(-4.741776E+04\right)\left(0.8828\right)+\left(6.274074E+04\right){\left(0.8828\right)}^2+\left(-2.516125E+04\right){\left(0.8828\right)}^3+\left(8.586987E+01\right)\left(15.369\right)+\left(6.843602E-01\right){\left(15.369\right)}^2+\left(-7.078907E-03\right){\left(15.369\right)}^3+\left(-1.207479E+02\right)\left(0.8828\right)\left(15.369\right)=20$ $\mathrm{Octane}\mathrm{Number}\left(\mathrm{ON}\right)=K_{\mathrm{ON}}+X1_{\mathrm{ON}}*\mathrm{DEN}+X2_{\mathrm{ON}}*{\mathrm{DEN}}^2+X3_{\mathrm{ON}}*{\mathrm{DEN}}^3+X4_{\mathrm{ON}}*\mathrm{FSMI}+X5_{\mathrm{ON}}*{\mathrm{FSMI}}^2+X6_{\mathrm{ON}}*{\mathrm{FSMI}}^3+X7_{\mathrm{ON}}*\mathrm{DEN}*\mathrm{FSMI}=\left(8.202192E+05\right)+\left(-2.845858E+06\right)\left(0.8828\right)+\left(3.290683E+06\right){\left(0.8828\right)}^2+\left(-1.268002E+06\right){\left(0.8828\right)}^3+\left(-1.182558E+01\right)\left(15.369\right)+\left(2.582860E-00\right){\left(15.369\right)}^2+\left(-1.277980E-01\right){\left(15.369\right)}^3+\left(0\right)\left(0.8828\right)\left(15.369\right)=52$
• Accordingly, as shown in the above example, indicative properties including cetane number, pour point, cloud point, aniline point, and aromaticity can be assigned to the crude oil samples without fractionation/distillation (crude oil assays).
• In alternate embodiments, the present invention can be implemented as a computer program product for use with a computerized computing system. Those skilled in the art will readily appreciate that programs defining the functions of the present invention can be written in any appropriate programming language and delivered to a computer in any form, including but not limited to: (a) information permanently stored on non-writeable storage media (e.g., read-only memory devices such as ROMs or CD-ROM disks); (b) information alterably stored on writeable storage media (e.g., floppy disks and hard drives); and/or (c) information conveyed to a computer through communication media, such as a local area network, a telephone network, or a public network such as the Internet. When carrying computer readable instructions that implement the present invention methods, such computer readable media represent alternate embodiments of the present invention.
• As generally illustrated herein, the system embodiments can incorporate a variety of computer readable media that comprise a computer usable medium having computer readable code means embodied therein. One skilled in the art will recognize that the software associated with the various processes described can be embodied in a wide variety of computer accessible media from which the software is loaded and activated. Pursuant to In re Beauregard, 35 U.S.P.Q.2d 1383 (U.S. Pat. No. 5,710,578), the present invention contemplates and includes this type of computer readable media within the scope of the invention. In certain embodiments, pursuant to In re Nuijten, 500 F.3d 1346 (Fed. Cir. 2007) (U.S. patent application Ser. No. 09/211,928), the scope of the present claims is limited to computer readable media, wherein the media is both tangible and non-transitory.
• The system and method of the present invention have been described above and with reference to the attached figures; however, modifications will be apparent to those of ordinary skill in the art and the scope of protection for the invention is to be defined by the claims that follow.

Claims (22)

We claim:

1. A system for evaluating a crude oil sample and calculating an indicative property of a naphtha or gas oil fraction of the crude oil sample without first distilling said naphtha or gas oil fraction, the system comprising:

a fluorometer that outputs fluorescence spectroscopy data;

a non-volatile memory device that stores calculation modules and data, the data including density of the crude oil sample and fluorescence spectroscopy data indicative of absorbance units at predetermined increments between a predetermined range for the oil sample, as derived by an analysis of the crude oil sample by the fluorometer;

a processor coupled to the non-volatile memory;

a first calculation module that retrieves the fluorescence spectroscopy data from the non-volatile memory device, calculates a crude oil fluorescence spectroscopy index value of the fraction from the absorbance units of the fluorescence spectroscopy data, and transfers the calculated crude oil fluorescence spectroscopy index value into the non-volatile memory; and

a second calculation module that calculates the indicative property for the naphtha or gas oil fraction of the crude oil from a two-variable polynomial equation with predetermined constant coefficients developed using linear regression techniques, and that stores the indicative property into the non-volatile memory device;

wherein the two variables of the two-variable polynomial equation are the crude oil fluorescence spectroscopy index and the density of the crude oil sample.

2. The system of claim 1, wherein the indicative property is the cetane number.

3. The system of claim 1, wherein the indicative property is the pour point.

4. The system of claim 1, wherein the indicative property is the cloud point.

5. The system of claim 1, wherein the indicative property is the aniline point.

6. The system of claim 1, wherein the indicative property is the aromaticity.

7. The system of claim 1, wherein the indicative property is the octane number.

8. The system of claim 1, wherein the temperature range for the fluorometer is 20-1000° C.

9. The system of claim 1, wherein the fluorescence spectroscopy index is that of whole crude oil.

10. The system of claim 1, wherein the fluorescence spectroscopy index is calculated from fluorescence spectroscopy data measured in the wavelength range of 250-800 nm.

11. The system of claim 1, wherein the fluorescence spectroscopy data is obtained directly from core and/or drill cuttings material.

12. A method for evaluating a crude oil sample and calculating an indicative property of a naphtha or gas oil fraction of the crude oil sample without first distilling said naphtha or gas oil fraction, the method comprising:

obtaining density of the crude oil sample;

providing a fluorometer that outputs fluorescence spectroscopy data

subjecting said crude oil sample to fluorescence spectroscopy analysis using the fluorometer, and entering absorbance units of the fluorescence spectroscopy data into non-volatile memory of a computer;

using a processor of the computer to calculate a crude oil fluorescence spectroscopy index value of the fraction from the absorbance units of the spectroscopy data; and

using the processor to calculate and enter into the non-volatile memory the indicative property for the naphtha or gas oil fraction of the crude oil from a two-variable polynomial equation with predetermined constant coefficients developed using linear regression techniques;

wherein the two variables of the two-variable polynomial equation are the crude oil fluorescence spectroscopy index and the density of the crude oil sample.

13. The method of claim 12, wherein the indicative property is the cetane number.

14. The method of claim 12, wherein the indicative property is the pour point.

15. The method of claim 12, wherein the indicative property is the cloud point.

16. The method of claim 12, wherein the indicative property is the aniline point.

17. The method of claim 12, wherein the indicative property is the aromaticity.

18. The method of claim 12, wherein the indicative property is the octane number.

19. The method of claim 12, wherein the temperature range for the fluorometer is 20-1000° C.

20. The method of claim 12, wherein the fluorescence spectroscopy index is that of whole crude oil.

21. The method of claim 12, wherein the fluorescence spectroscopy index is calculated from fluorescence spectroscopy data measured in the wavelength range of 250-800 nm.

22. The method of claim 12, wherein the fluorescence spectroscopy data is obtained directly from core and/or drill cuttings material.

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