WO1999058951A1 - Procede d'analyse du soufre reactif total - Google Patents

Procede d'analyse du soufre reactif total Download PDF

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Publication number
WO1999058951A1
WO1999058951A1 PCT/US1999/008460 US9908460W WO9958951A1 WO 1999058951 A1 WO1999058951 A1 WO 1999058951A1 US 9908460 W US9908460 W US 9908460W WO 9958951 A1 WO9958951 A1 WO 9958951A1
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WO
WIPO (PCT)
Prior art keywords
sulfur
reactive sulfur
fragment ions
mass
ion
Prior art date
Application number
PCT/US1999/008460
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English (en)
Inventor
Stilianos George Roussis
James Wade Fedora
Andrew Stuart Mcgill Cameron
Original Assignee
Exxon Research And Engineering Company
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 US09/076,539 external-priority patent/US5905195A/en
Application filed by Exxon Research And Engineering Company filed Critical Exxon Research And Engineering Company
Priority to CA002329818A priority Critical patent/CA2329818C/fr
Priority to EP99918639A priority patent/EP1078241A4/fr
Priority to JP2000548704A priority patent/JP2002514752A/ja
Publication of WO1999058951A1 publication Critical patent/WO1999058951A1/fr

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Classifications

    • 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
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • G01N30/7206—Mass spectrometers interfaced to gas chromatograph

Definitions

  • This invention relates to a method for analyzing for total reactive sulfur in crude oils or fractions thereof using mass spectrometric techniques.
  • total reactive sulfur (TRS) in crude oils due to the declining supplies of sweet crudes and the increasing need to process sour crudes.
  • TRS total reactive sulfur
  • the prediction of crude corrosivity is important to the economics of crude purchasing and processing. It is known that certain sulfur -containing species or total reactive sulfur are mainly responsible for the corrosivity attributed to sulfur compounds present in crude oils.
  • the total reactive sulfur includes contributions from the following sulfur- containing types: (i) hydrogen sulf ⁇ de, (ii) mercaptans, (iii) aliphatic sulfides, (iv) aliphatic disulfides, (v) elemental sulfur and (vi) polysulfides.
  • a combination of wet chemical methods are conventionally required for the determination of total reactive sulfur.
  • the aliphatic sulfides are determined by UV measurement of a sulfur-iodine complex. Mercaptans and hydrogen sulfide are measured by non-aqueous potentiometric titration. Disulfides are measured by conversion to mercaptans using acidic reduction. Polysulfides and elemental sulfur are determined by polaragraphic methods. The main concern of these chemical methods is the determination of aliphatic sulfides which are believed to account for the majority (about 80% or more) of total reactive sulfur species in crudes and fractions thereof. Since aliphatic sulfides contribute at least about 80% or more of the total corrosivity, any 2
  • the method for determining aliphatic sulfides was originally developed for the 450°F- fraction, and is based on the selective complexation of the "basic" sulfide sulfur atom with iodine.
  • the complex shows a strong band at 308 nm in the UV region.
  • this technique suffers from the disadvantage that iodine complexation can also occur with basic nitrogen- containing species which can affect the accuracy of the UV method of analysis.
  • This invention relates to a method for determining total reactive sulfur in a crude oil or fraction thereof which comprises the steps of: (1) introducing the crude oil or fraction thereof into a mass spectrometer;
  • fragment ions which are characteristic of reactive sulfur species including hydrogen sulfide, mercaptans, hydrocarbyl sulfides, hydrocarbyl disulfides, elemental sulfur and polysulfides, said fragment ions being selected from at least one of the group consisting of SH + , CSH + ;CH 3 S + , C 2 H 5 S + , H 2 S 2 + and
  • this invention relates to a method for determining total reactive sulfur as a function of boiling point for a crude oil or fraction thereof which comprises the steps of:
  • fragment ions which are characteristic of reactive sulfur species including hydrogen sulfide, mercaptans, hydrocarbyl sulfides, hydrocarbyl disulfides, elemental sulfur and polysulfides, said fragment ions being selected from at least one of the group consisting of SH + , CSH + , CH 3 S + , C 2 H 5 S + , H 2 S 2 + and S 2 + :
  • Figure 1 is a schematic showing reactions of parent molecular species which result in characteristic fragment ions.
  • Figure 2 is a graph showing the relative abundances of selected mass ions in the mass spectra of RSR and RSH compounds.
  • Figure 3 is a graph showing the relative abundances of selected mass ions in the mass spectra of RSSR compounds.
  • Figure 4 is a graph showing the relative abundances of selected mass ions in the mass spectra of thiophenes.
  • Figure 5 is a graph showing a total reactive sulfur external calibration curve using a Nigerian medium crude spiked with known amounts of reactive sulfur compounds.
  • Figure 6 is a graph showing a comparison of mass spectral areas and total reactive sulfur measured by standard wet chemical methods.
  • Figure 7 is a graph showing total reactive sulfur as a function of time/boiling point for three petroleum samples.
  • Figure 8 is a graph showing total sulfur as a function of time/boiling point for three petroleum samples. 6
  • Figure 9 is a graph showing a calibration chart of total reactive sulfur using model sulfur compounds.
  • Figure 10 is a graph showing a validation chart for the mass spectrometry total reactive sulfur method.
  • Crude oils and fractions thereof typically contain many different kinds of sulfur-containing species. These species are broadly characterized as being sulfur incorporated into an aromatic ring structure vs. non-aromatic sulfur.
  • Aromatic sulfur compounds such as thiophene and the like are generally not as corrosive when compared to non-aromatic sulfur-containing compounds such as mercaptans (RSH), hydrocarbyl sulfides (RSR) and hydrocarbyl disulfides (RSSR) wherein R is a hydrocarbyl radical.
  • hydrocarbyl is meant aliphatic, alicyclic, aromatic, aliphatic- and alicyclic-substituted aromatic, and aromatic- substituted aliphatic and alicyclic wherein the hydrocarbyl radicals may be substituted by halogen, nitro, cyano, carboxyl, amino and the like.
  • the nature of hydrocarbyl radical is not critical.
  • Total reactive sulfur is then the sum of the non-aromatic sulfur-containing species including the mercaptans, sulfides and disulfides identified above plus hydrogen sulfide, elemental sulfur and polysulfides (S x ).
  • mass spectrometer In the mass spectrometer, sample molecules are bombarded with high energy electrons thereby creating molecular ions which fragment in a pattern characteristic of the molecular species involved. A continuous series of mass spectra are obtained over a scan range of about 10 to 800 Daltons. The mass spectral data may also be acquired in selected ion monitoring mode. In this mode, care must be taken to select ions representative of the components of interest and to operate under repeatable conditions. A variety of mass spectrometers may be used including low resolution, high resolution, MS/MS, ion cyclotron resonance and time of flight.
  • Any ionization technique may be used such as electron ionization, chemical ionization, multiphotonionization, field desorption, field ionization and the like, provided that the technique provides either molecular or fragment ions which are suitable for use in the present method.
  • the ion m/z 47 is present in both RSR/RSH and RSSR spectra in approximately the same ratio, and is very weak in the spectra of the thiophenes.
  • the ion m/z 66 is more intense in the spectra of RSSR.
  • the ion CHS + (m z 44.9799) can be used to measure the total sulfur content in a sample. This approximation has been made previously by Gallegos, Anal. Chem., 1975, 45, 1 150 to monitor all sulfur compounds in fluid catalytic cracker heavy naphtha. However, this approximation includes both aromatic and non-aromatic sulfur-containing species. Ions C 2 H 5 S + (m/s 61.0112) and H 2 S 2 + (m/z 65.9598) can be used to monitor the amount of RSR RSH and RSSR, respectively.
  • CH 3 S + is very weak in thiophenes, and since it is approximately in the same ratio in both RSR RSH and RSSR, it can be used to quantitatively monitor the TRS content in a sample.
  • CH 3 S + (m/z 47) is the preferred fragment ion for quantitatively determining TRS.
  • the precise method of measuring TRS in a given sample may vary according to the type of mass spectrometer (MS) available.
  • MS mass spectrometer
  • a tandem MS/MS instrument can be used to directly measure TRS with maximum sensitivity.
  • High resolution (HR) 70 eV electron ionization can be used for the relative monitoring of the various sulfur types in crude oils and refinery streams. HR can attain more accurate results by using the response factors for each compound type.
  • concentrations of various sulfur types are obtained by HR measurement of ion abundances and a calibration matrix determined from known sulfur mixtures according to conventional methods.
  • HR can be coupled with a gas chromatograph to correlate TRS with boiling points for a given sample.
  • Low resolution (LR) 70 e V electron ionization can predict the concentration of sulfur species based on multiple linear regression analysis of samples with known concentrations of sulfur types. This method is the most practical for field measurements where more complex MS instruments are not available. Mass spectral data may be acquired in the selected ion monitoring (SIM) mode.
  • SIM selected ion monitoring
  • GC/MS utilizes a gas chromatograph interfaced with a mass spectrometer. While any chromatographic method may be used to separate the mixture into components, capillary gas chromatography is the preferred means for interfacing with a mass spectrometer.
  • the sample to be analyzed is first injected into a GC where the sample components are separated as a function of retention time and boiling point. Only partial chromatographic resolution of sample components is necessary. Components may also be identified by a detector such as a flame ionization detector, thermal conductivity detector, atomic emission detector or electron capture detector.
  • the separated or partially separated components are then transferred to the mass spectrometer by a heated capillary line interface. In this manner, a series of mass spectra can be obtained which are correlated with retention times and hence boiling point distribution of the sample under investigation. This provides a correlation of TRS species as a function of boiling point.
  • Mass spectra were obtained using a JEOL JMS-AX505WA double focusing MS.
  • This instrument contains an electrostatic sector (E) and a magnetic analyzer (B) in a forward geometry arrangement (Electric Field/Magnetic Field).
  • the JEOL MS instrument is based on a virtual image double focusing ion optics design with a 1 :4 image magnification. For a given resolution setting, the main slit width is four times wider than the collector slid width. The overall effect is to allow the entrance of a wider ion beam into the analyzer and thus increase the maximum sensitivity.
  • Samples were introduced into the MS through a heated inlet system, a Hewlett-Packard 5890 gas chromatograph or a dynamic batch type inlet system.
  • the dynamic batch system allows the direct introduction of the sample in a manner analogous to the sample introduction in a GC injection port using a carrier gas.
  • the advantages of this system are the short time required for analysis and the capabilities of automation using an autosampler for the routine analysis of samples.
  • This example is directed to the direct measurement of TRS using MS/MS.
  • CID spectra of various sulfur fragments were obtained at constant B/E scan using the instrument described in Example 1. This scan mode allows the acquisition of the daughter ions produced upon collisional dissociation of the selected parent ion structure.
  • the RSR RSH and RSSR transitions are bound by the relative abundance of each parent ion in the mixture and cannot therefore be used to directly monitor the amount of the corresponding sulfur type.
  • Fig. 5 shows an external calibration curve for TRS (standard addition).
  • TRS standard addition
  • Fig. 7 is a graph of TRS as a function of time for the three samples.
  • Fig. 8 is a graph of total sulfur as a function of time.
  • Fig. 9 is a graph of TRS using model sulfur compounds. Whole crudes, distillate and resid cuts are spiked with RSR and RSSR compounds. 16
  • Fig. 10 is a graph of the TRS difference measured by MS from the wet method for these samples.
  • the average difference from Fig. 10 is 0.0083 wt.%. This demonstrates that there is virtually no bias between LR MS and wet methods over a large set of data.
  • the LR MS method has the advantages that it is simple, rapid, precise and accurate and is amenable to refinery and field operations where expensive MS equipment is not available. Crudes with specific gravities between 0.75 and 1.10, and total sulfur values up to 7.0 S-wt.% have been successfully analyzed using this technique. The method is applicable to even wider ranges of crudes and fractions thereof.

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  • Physics & Mathematics (AREA)
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Abstract

L'invention porte sur un procédé visant à quantifier le soufre réactif total dans du pétrole brut ou une fraction de celui-ci à l'aide d'un spectromètre ou d'un chromatographe en phase gazeuse et d'un spectromètre de masse. La sélection des ions-fragments (1-4) caractéristiques de l'espèce de soufre total permet de déterminer de manière quantitative l'espèce de soufre réactif total. L'utilisation d'un spectromètre de masse basse résolution permet de quantifier rapidement le soufre réactif total dans le champ de pétrole ou sur des lieux éloignés où des instruments plus sophistiqués ne sont pas exploitables.
PCT/US1999/008460 1998-05-12 1999-04-16 Procede d'analyse du soufre reactif total WO1999058951A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002329818A CA2329818C (fr) 1998-05-12 1999-04-16 Procede d'analyse du soufre reactif total
EP99918639A EP1078241A4 (fr) 1998-05-12 1999-04-16 Procede d'analyse du soufre reactif total
JP2000548704A JP2002514752A (ja) 1998-05-12 1999-04-16 総反応性イオウの分析方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/076,539 US5905195A (en) 1996-09-12 1998-05-12 Method for analyzing total reactive sulfur
US09/076,539 1998-05-12

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WO1999058951A1 true WO1999058951A1 (fr) 1999-11-18

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JP (1) JP2002514752A (fr)
CA (1) CA2329818C (fr)
WO (1) WO1999058951A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9494536B1 (en) 2015-06-01 2016-11-15 Chevron U.S.A. Inc. Methods for predicting corrosion rate of crude oil derived samples using X-ray absorption spectroscopy
CN107709975A (zh) * 2015-04-08 2018-02-16 分子装置有限公司 荧光检测方法和系统
US10083825B2 (en) 2002-07-24 2018-09-25 Micromass Uk Limited Mass spectrometer with bypass of a fragmentation device
CN108693263A (zh) * 2018-04-27 2018-10-23 北京英力精化技术发展有限公司 一种含硫有机化学品中痕量单质硫的定量分析方法
US11971354B2 (en) 2015-04-08 2024-04-30 Molecular Devices, Llc Methods and systems for fluorescence detection using infrared dyes

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7075064B2 (en) * 2004-05-24 2006-07-11 Brigham Young University System and method for extracting spectra from data produced by a spectrometer
JP4626965B2 (ja) * 2004-11-16 2011-02-09 Ｊｘ日鉱日石エネルギー株式会社 硫黄化合物の分析方法
US7623946B2 (en) * 2005-09-12 2009-11-24 Exxonmobil Research And Engineering Company System and method that will synchronize data acquisition and modulation in a comprehensive two (multi) dimensional chromatography (separation) system to enable quantitative data analysis
US8975084B2 (en) * 2010-12-16 2015-03-10 Exxonmobil Research And Engineering Company Determination of cores or building blocks and reconstruction of parent molecules in heavy petroleums and other hydrocarbon resources

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5744702A (en) * 1996-09-12 1998-04-28 Exxon Research And Engineering Company Method for analyzing total reactive sulfur

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5744702A (en) * 1996-09-12 1998-04-28 Exxon Research And Engineering Company Method for analyzing total reactive sulfur

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1078241A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10083825B2 (en) 2002-07-24 2018-09-25 Micromass Uk Limited Mass spectrometer with bypass of a fragmentation device
CN107709975A (zh) * 2015-04-08 2018-02-16 分子装置有限公司 荧光检测方法和系统
US11971354B2 (en) 2015-04-08 2024-04-30 Molecular Devices, Llc Methods and systems for fluorescence detection using infrared dyes
US9494536B1 (en) 2015-06-01 2016-11-15 Chevron U.S.A. Inc. Methods for predicting corrosion rate of crude oil derived samples using X-ray absorption spectroscopy
CN108693263A (zh) * 2018-04-27 2018-10-23 北京英力精化技术发展有限公司 一种含硫有机化学品中痕量单质硫的定量分析方法

Also Published As

Publication number Publication date
CA2329818C (fr) 2007-12-11
EP1078241A4 (fr) 2007-07-25
EP1078241A1 (fr) 2001-02-28
JP2002514752A (ja) 2002-05-21
CA2329818A1 (fr) 1999-11-18

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