WO1996000380A1 - Determination de la presence de soufre dans des hydrocarbures par spectroscopie a l'infrarouge proche - Google Patents
Determination de la presence de soufre dans des hydrocarbures par spectroscopie a l'infrarouge proche Download PDFInfo
- Publication number
- WO1996000380A1 WO1996000380A1 PCT/US1994/007192 US9407192W WO9600380A1 WO 1996000380 A1 WO1996000380 A1 WO 1996000380A1 US 9407192 W US9407192 W US 9407192W WO 9600380 A1 WO9600380 A1 WO 9600380A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- absorbance
- process according
- hydrocarbon
- range
- organic sulfur
- Prior art date
Links
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 64
- 239000011593 sulfur Substances 0.000 title claims abstract description 64
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 54
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 53
- 238000004497 NIR spectroscopy Methods 0.000 title description 7
- 238000000034 method Methods 0.000 claims abstract description 75
- 238000002835 absorbance Methods 0.000 claims abstract description 50
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims description 50
- 239000002283 diesel fuel Substances 0.000 claims description 31
- 125000001741 organic sulfur group Chemical group 0.000 claims description 29
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 238000007620 mathematical function Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 4
- 238000001228 spectrum Methods 0.000 claims description 4
- 238000010998 test method Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims 2
- 238000004566 IR spectroscopy Methods 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 claims 1
- 150000002391 heterocyclic compounds Chemical class 0.000 claims 1
- 238000005259 measurement Methods 0.000 claims 1
- 150000002898 organic sulfur compounds Chemical class 0.000 claims 1
- 229920003987 resole Polymers 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 28
- 239000000446 fuel Substances 0.000 abstract description 11
- 238000009835 boiling Methods 0.000 abstract description 2
- 238000002953 preparative HPLC Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000004886 process control Methods 0.000 description 6
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 5
- 230000009102 absorption Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010743 number 2 fuel oil Substances 0.000 description 2
- -1 silica diamine Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000007619 statistical method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003269 fluorescent indicator Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000003987 high-resolution gas chromatography Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared 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
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
-
- 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
- G01N33/2835—Specific substances contained in the oils or fuels
- G01N33/287—Sulfur content
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
Definitions
- PIANO components in hydrocarbons by near infrared spectroscopy and is therefore related to the field of the present invention.
- the present invention relates to the determination of aromatic and/or organic sulfur constituents and/or color in hydrocarbons by near infrared spectroscopy and is generally classified in U.S. Patent Office Class 250, subclass 343, 341, and 339.
- European Patent Office 0285 251 filed 10/1988 relates to the general field of analysis by near infrared spectroscopy.
- Percents of each of the individual compounds detected by gas chromatography are grouped under their respective generic classifications in the PIANO classification system, and the relative percentage of each of the components paraffins through olefins is determined in weight percent, volume percent, or mole percent as required.
- An example of this procedure is that taught by Analytical Automation Specialists, Inc., "The Detailed Analysis of Petroleum Naphthas, Reformates, Gasoline and Condensates by High-Resolution Gas Chromatography", Operators Manual, P.O. Box 80653, Baton Rouge, Louisiana 70898. Also available is AAS (Analytical Automated Systems) PIANO Software Package, Sievers Research
- the absolute concentration of aromatics, color and/or sulfur is determined for mixtures with other hydrocarbons, preferably fuels, and most preferably diesel fuels, all grades, kerosene, fuel oils, all grades, light cycle oil, light vacuum oil, heating oils and vacuum oils as known in the petroleum industry.
- hydrocarbons preferably fuels, and most preferably diesel fuels, all grades, kerosene, fuel oils, all grades, light cycle oil, light vacuum oil, heating oils and vacuum oils as known in the petroleum industry.
- Standardization is an important feature of the present invention and is accomplished by separating the aromatics from the non- aromatics in the sample by use of well-known preparative high performance liquid chromatography, e.g. as described in Petroleum Derived Hydrocarbons, John D. Bacha, John W. Newman, and J. L. White, ACS Symposium series 303, Chapter 6.
- the concentration of the aromatics in the sample is then determined by measuring the absorbance of each of the two portions at the frequency being used (e.g. 1672 nm) and the absorbance of the aromatic fraction can be (but does not have to be) corrected by subtracting the absorbance of the non-aromatic fraction.
- Y mX + b + e
- the elements of the invention are therefore preferably the determination of aromatics content in hydrocarbons, preferably in the diesel no. 2 fuel oil boiling range by:
- the present invention can be utilized for most fuels, preferably for diesel fuel, and preferably by measuring absorbance at a frequency in the range of 800-2500 nm for aromatics, most preferably 1650-1700 nm or 2120-2256 nm for organic sulfur:
- the invention can be utilized as a batch process, in a flow-through cell, by the use of fiberoptic probes either bundled or single fiber, and the process control can be either feed-back or feed-forward based on the samples absorbance in the near-infrared, or optionally the first derivative of the samples absorbance or some other mathematical function of absorbance, being employed e.g. to operate a control valve.
- Figure 1 is a comparison of the repeatability error (% by absolute error) of four analytical methods for determining aromatics in diesel fuels (no. 2 fuel oil).
- the methods compared are fluorescent indicator absorption (FIA) by ASTM D-1319; mass spectroscopy (MS); super fluid chromatography (SFC) in which C02 above its critical pressure and temperature is used as the eluent; and near infrared according to the techniques of the present invention (NIR) for sets of 6 identical samples.
- FIA fluorescent indicator absorption
- MS mass spectroscopy
- SFC super fluid chromatography
- NIR near infrared according to the techniques of the present invention
- Figure 2 is a comparison of the percent aromatics determined in identical sets of 4 samples by heated FIA (a), heated FIA plus water deactivation of the chromatographic column (b), SFC (c); HPLC/DCD (high performance liquid chromatography using a dielectric constant-measuring detector) (d); and the NIR of the present invention (e). Note that results are expressed in volume percent for the two FIA methods and the HPLC/DCD method, whereas SFC and NIR results are expressed in weight percent. Note that NIR (except in sample no. 2) is closest to the average of all methods combined.
- FIG. 3 is a schematic diagram of a control system utilizing the
- NIR techniques of the present invention to control a refinery hydrogenation unit in which sufficient hydrogen is added not only to combine with the sulfur, but also sufficient to cause scisson and destruction of aromatics in diesel fuel.
- Figure 4 is a near infrared absorbance spectrum of the aromatic fraction of a diesel fuel which was obtained by HPLC.
- Figure 5 shows a schematic control system as detailed in Example 4.
- Figure 6 is a near infrared absorbance spectrum of a typical diesel fuel.
- Figure 7 is a plot showing the correlation observed at each wavelength from 1100-2500 nm for the aromatic content of diesel fuels using the techniques of the current invention. Note the superior correlation discovered at 1650 to 1700 nm and at 2120 to 2256 nm, most preferably 1654 to 1696 nm, or 2124 to 2252 nm, or both.
- Figure 8 is a near infrared (NIR) absorbance spectrum of the non-aromatic fraction of diesel fuel which was obtained by HPLC.
- NIR near infrared
- Figure 9 is a plot of multiple correlation vs. wavelength (nm) for organic sulfur.
- Figure 10 is a plot of NIR results vs. ASTM methods D1552 (Leco) and D3120 (microcoulometry) for determination for organic sulfur.
- a diesel fuel sample (6 grams) is separated into its aromatic and non-aromatic fractions by passing (@500 ml./minute) the fuel down a silica diamine column connected in series to a silica gel column using hexane as the solvent on a Waters Div. Millipore, Milford, Massachusetts, Model 500A high performance liquid chromatograph.
- the saturate fraction is collected off the end of the column and the hexane mobile phase is removed by rotary evaporation.
- the aromatics are then back flushed from the column by reversing the flow and substituting methylene chloride as the solvent.
- the solvent is again removed by rotary evaporation.
- the near infrared absorbance spectra of the non-aromatic and aromatic fractions are measured on an
- NIR Systems, Inc. Model 6500 spectrophotometer at 1672 nm and assigned concentrations of 0% and 100% aromatics by weight, respectively.
- EXAMPLE 2 (Flow-Through Mode) When the techniques of Example 1 are employed using fiberoptic probes to measure flowing streams and side streams in a refinery diesel fuel stream, accuracy approximately as good as obtained in the batch-process of Example 1 is achieved.
- Fiber optical probes preferably use the NIR range of 1650 to 1700 nm because of the cost and difficulty in obtaining non-absorbing fiber probes which transmit in the range of 2124 to 2252 nm.
- FIG. 3 schematically shows an important process control application of this invention.
- New diesel fuel regulations require that highway fuel produced after October, 1993, meet a maximum sulfur content specification.
- An NIR instrument calibrated as according to this invention, very close control of hydrotreater operation can be attained at minimum severity and hydrogen consumption.
- Raw feed, stream 300 flows through fired heater 310, feed /effluent exchanger 340, is admixed with hydrogen stream 320, through an adiabatic hydrotreating reactor 330, to tankage.
- the absorbance spectrum of the stream is measured by NIR probe 350, and this information provided to the process control computer 360.
- on-line NIR analysis allows maximum FCC LCO flow by maintaining constant analysis of the product diesel stream, providing information to the aforementioned process control computer 360 which adjusts FCC LCO flow 390 through flow control valve 400 such that the product stream just meets the required aromatics/cetane specification.
- This application is particularly attractive in that hydrotreating catalyst deactivation will be automatically compensated by the control loop by reducing the quantity of FCC LCO blended as the catalyst activity declines over the normal aging cycle.
- LOBS Low Odor Base Solvent
- An important feature of the invention is the discovery that sulfur, at least predominantly, is usually present in diesel fuel and heavier hydrocarbons as a derivative of benzothiophene.
- the C:S band of these thiophene or similar aromatic molecules can be observed by the NIR spectra of the present invention, despite the expectation that C:S would give a weak signal in comparison to C:H, due to the relative similarity of the carbon and sulfur molecular weights.
- the ratio of aromatics to sulfur in any given petroleum feedstock, e.g. diesel fuel can vary substantially because some of the aromatics will contain sulfur and is primarily present as derivatives of benzothiophene, a correlation can be made between the sulfur content and the aromatic content for any given feedstock.
- the invention can alternatively be used to directly compute the sulfur contained in each individual feedstock, or in the product if feed-back is being used, by monitoring the sulfur band itself which appears between 1584 and 1642 nm, and in some instances in the region 2036-2282 nm. As shown in Figure 9, this is a region where there is also almost perfect correlation with aromatic content. Thus, though there may be a distinct sulfur band in the 2036-2282 region, it appears that it is interfered with by the strong aromatic band, but this is not yet determined due to the difficulty in band assignments.
- on-line NIR analysis in the benzothiophenic band determines sulfur in the product diesel oil stream, providing information to the process control computer 360 which adjusts FCC LCO flow 390 through flow control valve 400 so that the product stream just meets the required maximum sulfur specification.
- this application is particularly attractive because the hydrotreating catalyst's gradual deactivation will be automatically compensated for by the control loop reducing the quantity of FCC LCO fed to the unit.
- sulfur we have found wavelengths in the ranges 850-900, 1118-1162, 1584-1642, 2036-
- Table A shows calibration results for forty samples which include one feed sample and 39 samples that have been hydrotreated at different severity. These samples span a diesel range of from 0.015 to 1.016 wt.% sulfur in diesel fuel. Sulfur was first determined by analysis by a Leco Sulfur Analyzer using ASTM D1552 procedure for high sulfur samples, and for low sulfur samples, sulfur was determined by a Dohrmann sulfur Microcoulometer using analytical procedures of ASTM D3120. These results are listed in Table A under "Lab %". Using the data of Table A, a correlation is developed against the laboratory test data.
- the NIR absorptions are measured and correlated using the wavelengths of 1620 nm, an analytical wavelength for benzothiophenic sulfur, and 2120 nm, combination band for aromatic and/or sulfur.
- a correlation "multiple R" of .9935 is obtained. This is an excellent correlation and is further confirmed by the regression constant K(0) equalling -0.177, remarkably close to 0, indicating a near absence of analytical interference. Similar results are obtained with diesel fuel, jet fuel, kerosene, lube oil, and FCC feedstock.
- a diesel fuel sample (6 grams) is separated into high sulfur and
- silica diamine column connected in series to a silica gel column using
- the low sulfur fraction is collected off the end of the column and the
- the high sulfur and low sulfur fractions are mixed in known
- a series of color standards are prepared by visually matching a
- the colors ranged from 1.0-5.5 in increments of 0.5.
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
Des combustibles hydrocarbures de distillat moyen, présentant de préférence des points d'ébullition initiaux supérieurs à 350 °F, sont séparés, par exemple, par un chromatographe liquide à haute performance préparatoire en fractions non aromatiques et aromatiques, lesquelles sont utilisées pour établir 0 % d'hydrocarbures aromatiques (les non aromatiques) et 100 % d'hydrocarbures aromatiques (les aromatiques) sur un spectrophotomètre à l'infrarouge proche. A partir d'absorbances par bandes d'hydrocarbures aromatiques à l'infrarouge proche d'échantillons inconnus, on détermine le pourcentage d'hydrocarbures aromatiques à l'aide de cet étalonnage à deux points et de l'équation de Beer-Lambert. Les bandes à l'infrarouge proches préférées de 1650 à 1700 et de 2120 à 2256 présentent une excellente corrélation avec la teneur en hydrocarbures aromatiques. De plus, des techniques similaires mesurent la quantité de soufre par corrélation avec la bande benzothiophénique ainsi que ses nuances et des bandes de combinaison ou éventuellement directement.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/626,132 US5145785A (en) | 1990-12-11 | 1990-12-11 | Determination of aromatics in hydrocarbons by near infrared spectroscopy and calibration therefor |
| EP91917609A EP0561789B1 (fr) | 1990-12-11 | 1991-08-29 | Determination des aromatiques presents dans des hydrocarbures a l'aide de la spectroscopie a infrarouge proche |
| AU86554/91A AU8655491A (en) | 1990-12-11 | 1991-08-29 | Determination of aromatics in hydrocarbons by near infrared spectroscopy |
| US07/839,982 US5370790A (en) | 1990-12-11 | 1992-02-20 | Determination of aromatics in hydrocarbons by near infrared spectroscopy |
| US07/942,117 US5348645A (en) | 1990-12-11 | 1992-09-08 | Determination of aromatics in hydrocarbons by near infrared spectroscopy |
| AU73174/94A AU7317494A (en) | 1990-12-11 | 1994-06-27 | Determination of sulfur in hydrocarbons by near infrared spectroscopy |
| GB9624259A GB2303918B (en) | 1994-06-27 | 1994-06-27 | Determination of sulfur in hydrocarbons by near infrared spectroscopy |
| PCT/US1994/007192 WO1996000380A1 (fr) | 1990-12-11 | 1994-06-27 | Determination de la presence de soufre dans des hydrocarbures par spectroscopie a l'infrarouge proche |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/626,132 US5145785A (en) | 1990-12-11 | 1990-12-11 | Determination of aromatics in hydrocarbons by near infrared spectroscopy and calibration therefor |
| CA002069392A CA2069392C (fr) | 1990-04-09 | 1992-05-25 | Methode et appareil pour l'analyse d'hydrocarbures par analyse dans le spectre presque infrarouge |
| PCT/US1994/007192 WO1996000380A1 (fr) | 1990-12-11 | 1994-06-27 | Determination de la presence de soufre dans des hydrocarbures par spectroscopie a l'infrarouge proche |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1996000380A1 true WO1996000380A1 (fr) | 1996-01-04 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1994/007192 WO1996000380A1 (fr) | 1990-12-11 | 1994-06-27 | Determination de la presence de soufre dans des hydrocarbures par spectroscopie a l'infrarouge proche |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO1996000380A1 (fr) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030071435A (ko) * | 2002-02-27 | 2003-09-03 | 백은기 | 화폐 및 인쇄용지 제조 방법 |
| WO2009037089A1 (fr) * | 2007-09-19 | 2009-03-26 | Siemens Aktiengesellschaft | Circuit de carburant conçu pour une unité flottante et procédé de fonctionnement associé |
| FR2934315A1 (fr) * | 2008-07-22 | 2010-01-29 | Peugeot Citroen Automobiles Sa | Dispositif et procede de commande de l'elimination d'oxydes de soufre, vehicule equipe de ce dispositif |
| CN103376242A (zh) * | 2012-04-25 | 2013-10-30 | 天津天士力之骄药业有限公司 | 一种芍药苷的检测方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987007721A1 (fr) * | 1986-06-05 | 1987-12-17 | Elf France | Systeme d'analyse du soufre dans les hydrocarbures liquides |
| US4800279A (en) * | 1985-09-13 | 1989-01-24 | Indiana University Foundation | Methods and devices for near-infrared evaluation of physical properties of samples |
| GB2217838A (en) * | 1988-04-15 | 1989-11-01 | Shell Int Research | Near infrared determination of petrophysical and petrochemical properties |
| WO1991015762A1 (fr) * | 1990-04-09 | 1991-10-17 | Ashland Oil, Inc. | Procede et appareil d'analyse d'hydrocarbures par spectroscopie dans l'infrarouge proche |
| WO1992010738A1 (fr) * | 1990-12-11 | 1992-06-25 | Ashland Oil, Inc. | Determination des aromatiques presents dans des hydrocarbures a l'aide de la spectroscopie a infrarouge proche |
| US5223715A (en) * | 1991-09-20 | 1993-06-29 | Amoco Corporation | Process for spectrophotometric analysis |
-
1994
- 1994-06-27 WO PCT/US1994/007192 patent/WO1996000380A1/fr active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4800279A (en) * | 1985-09-13 | 1989-01-24 | Indiana University Foundation | Methods and devices for near-infrared evaluation of physical properties of samples |
| US4800279B1 (fr) * | 1985-09-13 | 1991-11-19 | Indiana University Foundation | |
| WO1987007721A1 (fr) * | 1986-06-05 | 1987-12-17 | Elf France | Systeme d'analyse du soufre dans les hydrocarbures liquides |
| GB2217838A (en) * | 1988-04-15 | 1989-11-01 | Shell Int Research | Near infrared determination of petrophysical and petrochemical properties |
| WO1991015762A1 (fr) * | 1990-04-09 | 1991-10-17 | Ashland Oil, Inc. | Procede et appareil d'analyse d'hydrocarbures par spectroscopie dans l'infrarouge proche |
| WO1992010738A1 (fr) * | 1990-12-11 | 1992-06-25 | Ashland Oil, Inc. | Determination des aromatiques presents dans des hydrocarbures a l'aide de la spectroscopie a infrarouge proche |
| US5223715A (en) * | 1991-09-20 | 1993-06-29 | Amoco Corporation | Process for spectrophotometric analysis |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20030071435A (ko) * | 2002-02-27 | 2003-09-03 | 백은기 | 화폐 및 인쇄용지 제조 방법 |
| WO2009037089A1 (fr) * | 2007-09-19 | 2009-03-26 | Siemens Aktiengesellschaft | Circuit de carburant conçu pour une unité flottante et procédé de fonctionnement associé |
| US8360118B2 (en) | 2007-09-19 | 2013-01-29 | Siemens Aktiengesellschaft | Fuel system for a floating unit, and method for the operation thereof |
| FR2934315A1 (fr) * | 2008-07-22 | 2010-01-29 | Peugeot Citroen Automobiles Sa | Dispositif et procede de commande de l'elimination d'oxydes de soufre, vehicule equipe de ce dispositif |
| CN103376242A (zh) * | 2012-04-25 | 2013-10-30 | 天津天士力之骄药业有限公司 | 一种芍药苷的检测方法 |
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