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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 PDF

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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
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WIPO (PCT)
Prior art keywords
absorbance
process according
hydrocarbon
range
organic sulfur
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1994/007192
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English (en)
Inventor
Steven M. Maggard
William T. Welch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ashland LLC
Original Assignee
Ashland Oil Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/626,132 external-priority patent/US5145785A/en
Priority to US07/626,132 priority Critical patent/US5145785A/en
Priority to AU86554/91A priority patent/AU8655491A/en
Priority to EP91917609A priority patent/EP0561789B1/fr
Priority to US07/839,982 priority patent/US5370790A/en
Priority claimed from CA002069392A external-priority patent/CA2069392C/fr
Priority to US07/942,117 priority patent/US5348645A/en
Priority to AU73174/94A priority patent/AU7317494A/en
Priority to PCT/US1994/007192 priority patent/WO1996000380A1/fr
Priority to GB9624259A priority patent/GB2303918B/en
Application filed by Ashland Oil Inc filed Critical Ashland Oil Inc
Publication of WO1996000380A1 publication Critical patent/WO1996000380A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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 DEG 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.
PCT/US1994/007192 1990-12-11 1994-06-27 Determination de la presence de soufre dans des hydrocarbures par spectroscopie a l'infrarouge proche Ceased WO1996000380A1 (fr)

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
AU86554/91A AU8655491A (en) 1990-12-11 1991-08-29 Determination of aromatics in hydrocarbons by near infrared spectroscopy
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
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

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WO1996000380A1 true WO1996000380A1 (fr) 1996-01-04

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Cited By (4)

* Cited by examiner, † Cited by third party
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

Citations (6)

* Cited by examiner, † Cited by third party
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

Patent Citations (7)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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
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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