WO1999058951A1 - Procede d'analyse du soufre reactif total - Google Patents
Procede d'analyse du soufre reactif total Download PDFInfo
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- 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
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 54
- 239000011593 sulfur Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 47
- 150000002500 ions Chemical class 0.000 claims abstract description 69
- 239000012634 fragment Substances 0.000 claims abstract description 39
- 239000010779 crude oil Substances 0.000 claims abstract description 17
- 239000007843 reactive sulfur species Substances 0.000 claims abstract description 16
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 31
- -1 aromatic sulfur compounds Chemical class 0.000 claims description 25
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical compound [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 238000001819 mass spectrum Methods 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 229920001021 polysulfide Polymers 0.000 claims description 7
- 239000005077 polysulfide Substances 0.000 claims description 7
- 150000008117 polysulfides Polymers 0.000 claims description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000013375 chromatographic separation Methods 0.000 claims description 3
- 241000894007 species Species 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 150000003464 sulfur compounds Chemical class 0.000 description 8
- 229930192474 thiophene Natural products 0.000 description 8
- 238000002098 selective ion monitoring Methods 0.000 description 7
- 150000003577 thiophenes Chemical class 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000875 corresponding effect Effects 0.000 description 6
- 238000012417 linear regression Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000004885 tandem mass spectrometry Methods 0.000 description 5
- 238000001360 collision-induced dissociation Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002019 disulfides Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 238000000451 chemical ionisation Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- QQIIOKASUXUMMC-UHFFFAOYSA-N 2,3-dimethylthiophene Chemical compound CC=1C=[C]SC=1C QQIIOKASUXUMMC-UHFFFAOYSA-N 0.000 description 1
- GWQOOADXMVQEFT-UHFFFAOYSA-N 2,5-dimethyl thiophene Natural products CC1=CC=C(C)S1 GWQOOADXMVQEFT-UHFFFAOYSA-N 0.000 description 1
- RJJKOWNEOZAYHL-UHFFFAOYSA-N 2,5-dimethylthiophene Chemical compound CC1=C=C[C](C)S1 RJJKOWNEOZAYHL-UHFFFAOYSA-N 0.000 description 1
- HPEFYFPHOBNAST-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=[C]S1 HPEFYFPHOBNAST-UHFFFAOYSA-N 0.000 description 1
- 241001274237 Caranx latus Species 0.000 description 1
- CUDSBWGCGSUXDB-UHFFFAOYSA-N Dibutyl disulfide Chemical compound CCCCSSCCCC CUDSBWGCGSUXDB-UHFFFAOYSA-N 0.000 description 1
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 description 1
- LZAZXBXPKRULLB-UHFFFAOYSA-N Diisopropyl disulfide Chemical compound CC(C)SSC(C)C LZAZXBXPKRULLB-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- GOIGHUHRYZUEOM-UHFFFAOYSA-N [S].[I] Chemical compound [S].[I] GOIGHUHRYZUEOM-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002539 daughter ion scan Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical compound CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- AEDVWMXHRPMJAD-UHFFFAOYSA-N n,n,1,1,2,2,3,3,4,4,4-undecafluorobutan-1-amine Chemical compound FN(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AEDVWMXHRPMJAD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Food Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
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 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999058951A1 true WO1999058951A1 (fr) | 1999-11-18 |
Family
ID=22132660
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/008460 WO1999058951A1 (fr) | 1998-05-12 | 1999-04-16 | Procede d'analyse du soufre reactif total |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1078241A4 (fr) |
JP (1) | JP2002514752A (fr) |
CA (1) | CA2329818C (fr) |
WO (1) | WO1999058951A1 (fr) |
Cited By (5)
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)
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)
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 |
-
1999
- 1999-04-16 JP JP2000548704A patent/JP2002514752A/ja active Pending
- 1999-04-16 WO PCT/US1999/008460 patent/WO1999058951A1/fr active Application Filing
- 1999-04-16 EP EP99918639A patent/EP1078241A4/fr not_active Withdrawn
- 1999-04-16 CA CA002329818A patent/CA2329818C/fr not_active Expired - Fee Related
Patent Citations (1)
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)
Title |
---|
See also references of EP1078241A4 * |
Cited By (5)
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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