WO2016111986A1 - Caractérisation de pétrole brut par spectroscopie ultraviolet-visible - Google Patents
Caractérisation de pétrole brut par spectroscopie ultraviolet-visible Download PDFInfo
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- WO2016111986A1 WO2016111986A1 PCT/US2016/012144 US2016012144W WO2016111986A1 WO 2016111986 A1 WO2016111986 A1 WO 2016111986A1 US 2016012144 W US2016012144 W US 2016012144W WO 2016111986 A1 WO2016111986 A1 WO 2016111986A1
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- ultraviolet visible
- sample
- oil
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- 238000000870 ultraviolet spectroscopy Methods 0.000 title claims abstract description 20
- 239000010779 crude oil Substances 0.000 title claims description 73
- 238000012512 characterization method Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 55
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 18
- 239000003921 oil Substances 0.000 claims description 36
- 238000004364 calculation method Methods 0.000 claims description 15
- 238000002835 absorbance Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 239000002798 polar solvent Substances 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 10
- 230000006870 function Effects 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 230000003993 interaction Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000004611 spectroscopical analysis Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000003129 oil well Substances 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims 1
- 239000000523 sample Substances 0.000 description 18
- 238000003556 assay Methods 0.000 description 13
- 239000000446 fuel Substances 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000013500 data storage Methods 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000002798 spectrophotometry method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 150000002390 heteroarenes Chemical class 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- -1 bitumens Substances 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
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- 238000004590 computer program Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; Viscous liquids; Paints; Inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2811—Oils, i.e. hydrocarbon liquids by measuring cloud point or pour point of oils
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
- G01N2021/3155—Measuring in two spectral ranges, e.g. UV and visible
Definitions
- This invention relates to a method and process for the evaluation of samples of crude oil and its fractions by ultraviolet visible spectroscopy.
- 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, cycloparaffms, 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%.
- 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.
- 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 tme 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
- 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 determines the cetane number of diesel fuel oil; 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.
- 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 octane number 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.
- 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 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 D61 1 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 phases separate is recorded as the aniline point or mixed aniline point.
- UV-visible spectrophotometry which deals with electronic transitions within molecules, has traditionally provided unique information about aromatic and hetero aromatic compounds which absorb strongly in the UV region (200nm- 400nm). Despite this and owing to the complex molecular nature of crude oil, UV-visible spectra of these oils are often described as featureless, poorly defined spectra.
- Indicative properties e.g., cetane number, pour point, cloud point and aniline point
- Indicative properties e.g., cetane number, pour point, cloud point and aniline point
- the correlations also provide information about 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 performing the customary extensive and time-consuming crude oil assays.
- FIG. 1 is a graphic plot of typical ultraviolet visible spectroscopy data for three types of a crude oil sample solution prepared as described below;
- FIG. 2 is a process flow diagram of steps carried out to establish a value for indicative properties of a gas oil fraction, using the system and method herein;
- FIG. 3 is a block diagram of components of a system for implementing the invention according to one embodiment.
- a system and method for determining one or more indicative properties of a hydrocarbon sample.
- Indicative properties e.g., cetane number, pour point, cloud point and aniline point
- cetane number, pour point, cloud point and aniline point are assigned as a function of data obtained from ultraviolet visible spectroscopy data of a crude oil sample and the density of the crude oil sample.
- the correlations provide information about gas oil and/or naphtha indicative 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 performing the customary extensive and time-consuming crude oil assays.
- the currently used crude oil assay method is costly in terms of money and time. It costs about $50,000 US and takes two months to complete one assay. With the method and system herein, the crude oil can be classified as a function of NMR data, and thus decisions can be made for purchasing and/or processing.
- 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.
- Samples can be obtained from various sources, including an oil well, stabilizer, extractor, or distillation tower.
- spectra are obtained by a suitable known or to be developed UV-visible spectrophotometry techniques
- UV-visible spectrophotometry is carried out on a sample of crude oil according to the method and system herein to provide unique information about aromatic and heteroaromatic compounds which absorb strongly in the UV region (200nm-400nm).
- Specific individual aromatic compounds and components have maxima at well-defined wavelengths.
- Wavelength maxima of known aromatic compounds and components are evaluated and extracted from the UV spectra of crude oils. These maxima are used to formulate indices for the aromatic content of the crude oil.
- These indices are used to assign one or more indicative properties of the oil, e.g., cetane number, pour point, cloud point and aniline point.
- this information can be obtained relatively rapidly and inexpensively from a UV-visible scan as compared to the prior art assay methods described above.
- FIG. 2 shows a process flowchart in a method according to one embodiment herein.
- Crude oil samples are prepared and analyzed by ultraviolet visible spectrophotometry between 200-500 nm, in certain embodiments between 220-400 nm.
- a crude oil sample is weighed.
- solutions are prepared by dissolving a sample of the crude oil in a two-part solvent system of a paraffmic solvent having from 5-20 carbon atoms and a polar solvent, e.g., at a ratio of 90: 10 % v/v.
- effective paraffmic solvents include iso-octane.
- effective polar solvents include dichloromethane.
- a polar solvent prevents precipitation of asphaltenes from the crude oil sample and ensures that all solutions are translucent for the measurement.
- the polar solvents are selected based on their Hildebrand solubility factors or their two-dimensional solubility parameters.
- the overall Hildebrand solubility factor is a well known measure of polarity and has been calculated for numerous compounds. See, for example, the Journal of Paint Technology, Vol. 39, No. 505 (February 1967).
- the solvents can also be described by their two-dimensional solubility parameter. See, for example, I. A. Wiehe, "Polygon Mapping with Two-Dimensional Solubility Parameters", I&EC Research, 34, 661-673 (1995).
- the complexing solubility parameter component which describes the hydrogen bonding and electron donor-acceptor interactions, measures the interaction energy that requires a specific orientation between an atom of one molecule and a second atom of a different molecule.
- the field force solubility parameter which describes the van der Waals and dipole interactions, measures the interaction energy of the liquid that is not destroyed by changes in the orientation of the molecules.
- the UV absorbance of the crude oil solutions is determined, for instance, in a conventional one cm quartz cell.
- the absorbance values of the samples are summed at predetermined increments (e.g., even numbers, odd number, or increments of any number) between a predetermined range, e.g., between 200-500 nm, in certain embodiments between 220-400 nm to calculate the characterization index.
- predetermined increments e.g., even numbers, odd number, or increments of any number
- a predetermined range e.g., between 200-500 nm, in certain embodiments between 220-400 nm to calculate the characterization index.
- one or more samples of crude oil in dilute solution are analyzed by UV- visible spectrophotometry over the wavelengths 200-500 nm, in certain embodiments 220-400 nm.
- step 240 the density and spectra data are entered into a computer.
- step 250 the CUVISI is calculated.
- Equation (1 ) shows a crude oil ultraviolet visible index, CUVISI.
- Absorbance absorbance value of the prepared crude oil sample solution at a specific wavelength over the range L to H at intervals of N, whereby in certain embodiments L is between about 200 nm and 220 nm and H is between 400 nm and 500 nm, and N is between 1 and 3, and x is the weight of the sample used, in mg.
- Equations (2) through (5) show, respectively, the cetane number, pour point, cloud point and aniline point of gas oils boiling in the range 180-370 °C that can be predicted from the density and ultraviolet visible spectroscopy index (CUVISI) of crude oils.
- the cetane number is calculated.
- the pour point is calculated.
- the cloud point is calculated.
- the aniline point is calculated. While FIG. 2 shows steps 260 through 290 performed sequentially, they can be performed in any order, and in certain embodiments fewer than all can be calculated and assigned.
- pour Point (PP) PP + X1 PP * DEN + X2 PP * DEN 2 + X3 PP * DEN 3 + X4p P * (CUVISI/100) + X5 PP * (CUVISI/100) 2 + X6p P * (CUVISI/100) 3 +
- Cloud Point (CP) K CP + Xl C p * DEN + X2 C p * DEN 2 + X3 C p * DEN 3 +
- Aniline Point (AP) K AP + XI A p * DEN + X2 AP * DEN 2 + X3 A p * DEN 3 +
- DEN density of the crude oil sample
- CUVISI crude oil UV visible index
- KCET XI CET— X7CET, KPP, Xl pp-X7pp, Kcp, Xlcp— 7CP, A p, and ⁇ 1 ⁇ ⁇ - ⁇ 7 ⁇ are constants that were developed using linear regression techniques
- Computer system 300 includes a processor 310, such as a central processing unit, an input/output interface 320 and support circuitry 330.
- a display 340 and an input device 350 such as a keyboard, mouse or pointer are also provided.
- the display 340, input device 350, processor 310, input/output interface 320 and support circuitry 330 are shown connected to a bus 360 which also connects to a memory unit 370.
- Memory 370 includes program storage memory 380 and data storage memory 390.
- computer 300 is depicted with the direct human interface components of display 340 and input device 350, programming of modules and importation and exportation of data can also be accomplished over the interface 320, for instance, where the computer 300 is connected to a network and the programming and display operations occur on another associated computer, or via a detachable input device, as are well known in the art for interfacing programmable logic controllers.
- Program storage memory 380 and data storage memory 390 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 380 and data storage memory 390 can be embodied in a single memory device or separated in plural memory devices.
- Program storage memory 380 stores software program modules and associated data, and in particular stores a crude oil UV visible index (CUVISI) calculation module 381 and one or more indicative property calculation modules 382-385 such as a cetane number calculation module 382, a pour point calculation module 383, a cloud point calculation module 384, and an aniline point calculation module 385.
- CUVISI crude oil UV visible index
- Data storage memory 390 stores data used and/or generated by the one or more modules of the present invention, including but not limited to density of the crude oil sample, UV absorbance data or portions thereof used by the one or more modules of the present system, and calculated indicative properties generated by the one or more modules of the present system.
- the computer system 300 can be any general or special purpose 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 300 is shown, for illustration purposes, as a single computer unit, the system can comprise a group/farm of computers which can be scaled depending on the processing load and database size, e.g., the total number of samples that are processed and results maintained on the system. The computer system 300 can serve as a common multi-tasking computer.
- Computer system 300 preferably supports an operating system, for example stored in program storage memory 390 and executed by the processor 310 from volatile memory.
- the operating system contains instructions for interfacing the device 300 to the calculation module(s).
- the operating system contains instructions for interfacing computer system 300 to the Internet and/or to private networks.
- K C ET Exemplary constants K C ET, X CE T X7CET, pp, Xlpp-X7pp, Kcp, Xlcp-XVcp, K ;
- the instrument is allowed to warm up for 30 minutes prior to analysis and is auto-zeroed without cells in both sample and reference beams.
- the reference cell is filled with the solvent mixture then placed in the reference beam.
- Solutions of the crude oil sample solutions prepared as described above are successively placed in a clean quartz sample cell and the spectra are recorded against the reference solvent blank. The spectra are recorded at a scan speed of 100 nm/min with a fast response time.
- Equation (1) is applied and the data recorded in Table 4 for the sample of Arab medium crude oil produces a CUVISI of 94.9748. Applying equation (2) and the constants from Table 3,
- Cetane Number (CET) K CE T + XI GET * DEN + X2 CE T * DEN 2 +
- Cloud Point (CP) CP + XI CP * DEN + X2 CP * DEN 2 + X3 C p * DEN 3 +
- Aniline Point (AP) K AP + XI AP * DEN + X2 A p * DEN 2 + X3 A p * DEN 3 +
- indicative properties including cetane number, pour point, cloud point and aniline point can be assigned to the crude oil samples without fractionation/distillation (crude oil assays).
- the present invention can be implemented as a computer program product for use with a computerized computing system.
- 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., readonly 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.
- non-writeable storage media e.g., readonly memory devices such as ROMs or CD-ROM disks
- writeable storage media e.g., floppy disks and hard drives
- communication media such as a local area network, a telephone network, or a public network such as the Internet.
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Abstract
Système et procédé destinés au calcul et à l'attribution d'une valeur indicative (par exemple, un indice de cétane, un point d'écoulement, un point trouble et un point d'aniline) d'une fraction d'un échantillon de pétrole sur la base d'un indice calculé et attribué à partir de données de spectroscopie ultraviolet-visible de l'échantillon de pétrole.
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US15/060,230 US10048194B2 (en) | 2012-02-21 | 2016-03-03 | Characterization of crude oil by ultraviolet visible spectroscopy |
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US201562099723P | 2015-01-05 | 2015-01-05 | |
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US13/400,865 Continuation-In-Part US9285307B2 (en) | 2010-10-18 | 2012-02-21 | Characterization of crude oil by ultraviolet visible spectroscopy |
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CA2781273A1 (fr) * | 2012-06-28 | 2013-12-28 | Imperial Oil Resources Limited | Diluant pour diluer des hydrocarbures visqueux |
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US5710578A (en) | 1987-12-09 | 1998-01-20 | International Business Machines Corporation | Computer program product for utilizing fast polygon fill routines in a graphics display system |
US5656810A (en) * | 1993-11-22 | 1997-08-12 | The Research Foundation Of City College Of New York | Method and apparatus for evaluating the composition of an oil sample |
US20030195708A1 (en) * | 2001-11-30 | 2003-10-16 | Brown James M. | Method for analyzing an unknown material as a blend of known materials calculated so as to match certain analytical data and predicting properties of the unknown based on the calculated blend |
US20070231912A1 (en) * | 2001-11-30 | 2007-10-04 | Reischman Paul T | Method for determining asphaltenes contamination in used marine engine lubricants using UV-visible spectroscopy and chemometrics |
US20070295640A1 (en) * | 2006-06-26 | 2007-12-27 | Schlumberger Technology Corporation | Compositions and Methods of Using Same in Producing Heavy Oil and Bitumen |
US20100113311A1 (en) * | 2006-12-28 | 2010-05-06 | United Technologies Corporation | Method for quantitatively determining the dye content in dyed oils |
US20110152136A1 (en) * | 2008-04-23 | 2011-06-23 | Trevor Hughes | Solvent assisted oil recovery |
CA2781273A1 (fr) * | 2012-06-28 | 2013-12-28 | Imperial Oil Resources Limited | Diluant pour diluer des hydrocarbures visqueux |
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