EP2044613A2 - Procédé et système pour la caractérisation chimique et physique d'échantillons complexes - Google Patents

Procédé et système pour la caractérisation chimique et physique d'échantillons complexes

Info

Publication number
EP2044613A2
EP2044613A2 EP07835930A EP07835930A EP2044613A2 EP 2044613 A2 EP2044613 A2 EP 2044613A2 EP 07835930 A EP07835930 A EP 07835930A EP 07835930 A EP07835930 A EP 07835930A EP 2044613 A2 EP2044613 A2 EP 2044613A2
Authority
EP
European Patent Office
Prior art keywords
sample
constituents
column
gas
injector
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.)
Pending
Application number
EP07835930A
Other languages
German (de)
English (en)
Other versions
EP2044613A4 (fr
Inventor
Joaquin A. Lubkowitz
Aaron Mendez
Roberto I. Meneghini
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.)
Separation Systems Inc
Original Assignee
Separation Systems 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
Application filed by Separation Systems Inc filed Critical Separation Systems Inc
Publication of EP2044613A2 publication Critical patent/EP2044613A2/fr
Publication of EP2044613A4 publication Critical patent/EP2044613A4/fr
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components

Definitions

  • the present invention relates to a method and system for rapid determination of composition, of crude oils and fractions thereof, as well as other substances and obtaining the information necessary to assess the yield of commercially valuable fuel and lube oil fractions, for example, in a single process.
  • the present invention is directed to a method and system for determining yields and compositions in terms of a simultaneous boiling point distributions and hydrocarbon types breakdown, across the boiling range of interest, and determining the changes in chemical composition and yields in upgrading and/or conversion processes, compiling a preliminary evaluation of a variety of geochemical parameters or biomarkers for the correlation to fingerprint identification, maturity, origins, etc., and compiling experimental data to chemical and physical properties.
  • Gas Chromatography is a chemical analysis instrument for separating chemicals in a complex sample.
  • a gas chromatograph uses a narrow tube, known as a column, through which different chemical constituents of a sample pass in a gas stream.
  • the gas stream is also called the carrier gas or mobile phase.
  • Gas Liquid Chromatography (GLC), or simply Gas Chromatography (GC) is a type of chromatography in which the mobile phase is a gas.
  • the chemical constituents within the sample pass through the column at different rates, depending on their various chemical and physical properties and their interaction with a specific column phase .
  • This column phase is called the stationary phase and is a microscopic layer of liquid on an inert solid support in the column. If the phase is bonded directly to the tubing it is called a capillary column
  • the column is often flexible so that a very long column can be wound into a small coil.
  • the column(s) in a GC are contained in an oven, the temperature of which is precisely controlled (e.g., electronically).
  • the rate at which a sample passes through the column is directly proportional to the temperature of the column. The higher the column temperature, the faster the sample moves through the column. However, when a sample moves quickly through the column, it interacts less with the stationary phase, and the analytes are less separated.
  • the stationary phase separates the different components, causing each one to exit the column at a different time, which is called the retention time.
  • Other parameters can also be used to alter the order or time of the retention, such as the carrier gas flow rate and the temperature as well as the chemical nature of the phase..
  • the present invention solves the above-identified needs, as well as others by providing methods and systems for rapid determination of composition of crude oils and fractions thereof, as well as other substances, and in a single process obtaining the information necessary to assess the yield of commercially valuable petroleum fuel and lube oil fractions using Gas Chromatography - FID/Mass Spectrometry.
  • Variations of the present invention also include auto sampler features, a wall coated capillary column, a temperature programmable injector and data processing features for compiling and processing experimental data.
  • Embodiments of the present invention further include a computer system with application software and a communication network.
  • the present invention in one embodiment, provides a graphical user interface for the entry of data, and for displaying information, such as in a graphical manner, to show the relationship of various determined outputs and results.
  • the present invention enables multidimensionality with simple hardware, wherein a low resolution column is sufficient for analyses and additional highly resolving techniques are not required.
  • the present invention provides hydrocarbon type analysis and Simulated Distillation ("SimDis”) data, including providing such analysis and data in a single process.
  • SimDis Simulated Distillation
  • Figure 1 shows a diagram of an exemplary Gas Chromatography —
  • GC-FID/MS FID/Mass Spectrometry apparatus
  • Figure 2 illustrates a block diagram of various exemplary computer system components for use in accordance with one embodiment of the present invention
  • Figure 3 shows an exemplary communication system of the present invention for use with the computer system 1 of Figure 2.
  • Figure 3B shows a flow chart of an exemplary method according to an embodiment of the present invention.
  • Figure 4 shows the results of a sample analyzed in accordance with a method and system of an embodiment of the present invention.
  • Figure 5 shows results for three injections of a similar material analyzed according to a method and system of an embodiment of the present invention.
  • Figure 6 shows results for three injections of a similar material analyzed according to a method and system of an embodiment of the present invention.
  • Figure 7 shows a retention time standard for ASTM D 7169-2005.
  • Figure 8 shows a crude oil boiling point calibration curve.
  • Figure 9 shows the measured results of a reference material.
  • Figure 10 shows the measured results for a crude oil sample.
  • Figure 11 shows algorithms for aroma tics and saturates.
  • Figure 12 shows a group type analysis of compounds that may be found within crude oil.
  • Figure 13 shows a retention time calibration standard useable in accordance with embodiments of the present invention.
  • Figure 14 shows a whole crude oil analysis useable in accordance with embodiments of the present invention.
  • Figure 15 shows experimental results of a measured fraction analyzed in accordance with methods and systems of embodiments of the present invention.
  • Figure 16 shows the signal overlapping from fractions, along with crude oil, produced using analysis in accordance with methods and systems of embodiments of the present invention.
  • Figure 17 shows an analysis of Fraction #1, as analyzed according to a method and system of an embodiment of the present invention.
  • Figure 18 shows an analysis of Fraction #1 cut in whole crude, as analyzed according to a method and system of an embodiment of the present invention.
  • Figure 19 shows the results of a sample of paraffinic light crude oil, as analyzed according to a method and system of an embodiment of the present invention.
  • Figure 20 shows the results of a sample of paraffinic crude oil, as analyzed according to a method and system of an embodiment of the present invention.
  • Figure 21 shows the results for samples of lube oil fractions, as analyzed according to a method and system of an embodiment of the present invention.
  • Figure 22 shows a hydrocarbon type analysis from a whole crude sample, as analyzed according to a method and system of an embodiment of the present invention.
  • Figure 23 shows a hydrocarbon type analysis from a whole crude sample, produced in accordance with a method and system of an embodiment of the present invention.
  • Figure 24 shows a comparative study of middle hydrocarbon samples, as analyzed according to a method and system of an embodiment of the present invention.
  • Figures 25-51 contain various data and other information produced using systems and methods of the present invention.
  • FIG. 1 therein shown is the general architecture of an exemplary Gas Chromatography — FID/Mass Spectrometry apparatus (GC- FID/MS), as used in accordance with a method and system of the present invention.
  • GC- FID/MS Gas Chromatography — FID/Mass Spectrometry apparatus
  • the GC-FID/MS of Figure 1 includes a gas chromatograph (100), which includes an injector (200), a column (300), and an oven (400); a mass spectrometer (MS) (600); a flame ion detector (FID) (500); a divider (700); and a data processing system for acquiring and processing the data.
  • a gas chromatograph 100
  • MS mass spectrometer
  • FID flame ion detector
  • divider 700
  • a data processing system for acquiring and processing the data.
  • One variation provides a graphical user interface for the entry of data and for displaying information, such as in a graphical manner, to show the relationship of various determined outputs and results.
  • the GC-FID/MS may also include an automatic liquid sampler (ALS).
  • the column may be a wall coated capillary column, and the inlet may be a temperature programmable injector.
  • the gas chromatograph (100) utilizes the difference in chemical properties between different chemical constituents in a sample to separate the chemical constituents. As the different chemical constituents exit the gas chromatograph at different times, the mass spectrometer, which is located downstream in the gas flow, evaluates the chemical constituents separately and is able to identify the constituents.
  • the mass spectrometer (600) identifies the various chemical constituents that pass through it at a flow D2 by breaking each constituent into ionized fragments and detecting these fragments using the mass to charge ratio of the fragments.
  • the FID (500) is, for example, an ion detector that uses an air- hydrogen flame to produce ions. As the chemical constituents in the sample exit the gas chromatograph at a flow D1, they pass through the flame and are burned, producing ions. The ions then produce an electric current, which is used to provide the signal output of the FID.
  • the FID of some embodiments can only detect components that can be burned, and the FID destroys the components during detection. Thus, no further detection is made after the FID completes processing.
  • the nature and amount of constituents that flow through the mass spectrometer 600 and through the FID 500 may be similar in order to combine the results obtained by the MS 600 and by the FID 500.
  • the apparatus of this embodiment of the present invention also includes a divider (700) that divides the exiting chemical constituent between the FID and the MS, so that portions of the exiting chemical constituent are analyzable by both the FID and MS simultaneously.
  • the divider 700 should be able to prevent molecule discrimination in the constituents and distribute the constituents equally between the flow D1 and the flow D2, which is achieved by heating the constituents at a temperature necessary to ensure that no molecular discrimination occurs.
  • pneumatic control module may be part of the GC-FID/MS, that controls the pressure of the sample as it passes through the divider in order to preserve an equal ratio of constituents flowing through D1, and another PCM that controls the pressure of the sample as it passes through the divider in order to preserve an equal ratioof constituents flowing through D2, so that the amount of constituents that pass through D1 is about equal to the amount of constituents that pass through D2.
  • the divider may be or include a micro influx divider.
  • An exemplary embodiment, of the present invention uses a megabore capillary high throughput column and a temperature programmable injector.
  • the column includes a capillary column element that is about 5 m by 0.53 mm i.d.
  • the FID detector is an FID 440 Celsius
  • the carrier gas is Helium at a constant flux rate of about 12 mL/min
  • the oven is programmed to start at about 40° Celsius, to raise about 10° Celsius/min until about 430° Celsius is reached, to maintain the temperature for about 12 minutes, with an equilibrium time of about two minutes
  • the injection volume is about 0.2 ⁇ L
  • the dilution is about 2% in CS2.
  • hydrogen could be used instead of helium as the carrier gas.
  • the GC-FID/MS may be used to analyze the physical and chemical characterization of petroleum fractions.
  • a rapid determination may be made of the composition of crude oils, for example.
  • This apparatus and method may also be applied to fractions of crude oil, or other substance. Information necessary to access the yield of commercially available valuable fuel and lube oil fractions can also be obtained in a single process.
  • the mass spectral data may be converted to weight and volume percent chemical composition.
  • the system and method provide the boiling point distribution and chemical composition of the analyzed substance based on saturate and aromatic group types.
  • Crude oil may contain a mixture of chemical compounds from a family of several hundred chemical compounds. Some chemicals that may be found in crude oil include hexane, jet fuels fraction, diesel fractions, benzene, toluene, xylenes, naphthalene, and fluorine, in addition to other petroleum products such as heavy diesel, atmospheric residues, vacuum residues and gasoline naphtha to be used in gasolines..
  • the characterization of complex fractions and versatility are improved by combining the signals of the FID detector and the mass spectrometer detector in a single processing apparatus.
  • the signal from the FID detector is in the simulated distillation mode and the MD detector is in a single environment of synergistic mode.
  • the MD detector provides ion fragmentation at continuous time intervals during the elution of the sample though the column
  • the present invention thus is able to provide a powerful analytical tool allowing the simultaneous physical and chemical characterization of whole crude oil samples and their fractions, without the need to perform the physical separation of the hydrocarbon fractions.
  • the FID detector is in a simulated distillation mode.
  • Simulated distillation is a gas chromatography technique that separates individual hydrocarbon components in their order of boiling points and is used to simulate the time-consuming laboratory-scale physical distillation procedure referred to as true boiling point distillation.
  • an FID is used for detection and measurement of the hydrocarbon analytes.
  • the result of SimDis analysis provides a distillation curve which is a quantitative percent mass yield as a function of boiling point of the hydrocarbon components of the sample.
  • the present invention conforms with the
  • ASTM American Society for Testing and Materials
  • D-2887, D-6352, and D-7169 standards for stimulated distillation: D-2887, D-6352, and D-7169.
  • Simulated distillation is a proven and accepted technique for the physiochemical characterization of crude and fractions of oil.
  • ASTM D2 accepted a new method for the analysis of fractions with a final boiling point of 615 Celsius (C5 to C60). See ASTM D 7213-05.
  • Mass spectrometry reports a composition in the basis of five principal groups: paraffin, napthalene, aromatic, sulfur, and non-identified. All of the ASTM methods, with the exception of those applying to napthalenes, require a chromatographic separation of the saturated and aromatics. Such separation requires high resolution methods. High resolution requires complex and costly equipment. New multidimensional analytical mechanisms, such as GC x GC and GC-MS-TOF, also require complex instruments and procedures, even for the gasoline range.
  • the present invention enables spectrometric analysis within fractions at a low resolution. Thus, it allows simple and quick analysis.
  • Figure 2 illustrates a block diagram of various computer system components useable with an exemplary implementation of a physical and chemical characterization of petroleum fractions by GC/SIMDIS/MS, in accordance with embodiments of the present invention.
  • the controller of the present invention may be implemented using hardware, software or a combination thereof and may be implemented in one or more computer systems or other processing systems. In one embodiment, the invention is directed toward one or more computer systems capable of carrying out the functionality described herein.
  • FIG. 2 shows a computer system 1 that includes one or more processors, such as processor 4.
  • the processor 4 is connected to a communication infrastructure 6 (e.g., a communications bus, cross-over bar, or network).
  • a communication infrastructure 6 e.g., a communications bus, cross-over bar, or network.
  • Computer system 1 can include a display interface 2 that forwards graphics, text, and other data from the communication infrastructure 6 (or from a frame buffer not shown) for display on the display unit 30.
  • Computer system 1 also includes a main memory 8, preferably random access memory (RAM), and may also include a secondary memory 10.
  • the secondary memory 10 may include, for example, a hard disk drive 12 and/or a removable storage drive 14, representing a floppy disk drive, a magnetic tape drive, an optical disk drive, etc.
  • the removable storage drive 14 reads from and/or writes to a removable storage unit 18 in a well known manner.
  • Removable storage unit 18, represents a floppy disk, magnetic tape, optical disk, etc., which is read by and written to removable storage drive 14.
  • the removable storage unit 18 includes a computer usable storage medium having stored therein computer software and/or data.
  • secondary memory 10 may include other similar devices for allowing computer programs or other instructions to be loaded into computer system 1.
  • Such devices may include, for example, a removable storage unit 22 and an interface 20. Examples of such may include a program cartridge and cartridge interface (such as that found in video game devices), a removable memory chip (such as an erasable programmable read only memory (EPROM), or programmable read only memory (PROM)) and associated socket, and other removable storage units 22 and interfaces 20, which allow software and data to be transferred from the removable storage unit 22 to computer system 1.
  • EPROM erasable programmable read only memory
  • PROM programmable read only memory
  • Computer system 1 may also include a communications interface 24.
  • Communications interface 24 allows software and data to be transferred between computer system 1 and external devices.
  • Examples of communications interface 24 may include a modem, a network interface (such as an Ethernet card), a communications port, a Personal Computer Memory Card International Association (PCMCIA) slot and card, etc.
  • Software and data transferred via communications interface 24 are in the form of signals 28, which may be electronic, electromagnetic, optical or other signals capable of being received by communications interface 24. These signals 28 are provided to communications interface 24 via a communications path (e.g., channel) 26.
  • This path 26 carries signals 28 and may be implemented using wire or cable, fiber optics, a telephone line, a cellular link, a radio frequency (RF) link and/or other communications channels.
  • RF radio frequency
  • computer program medium and “computer usable medium” are used to refer generally to media such as a removable storage drive 14, a hard disk installed in hard disk drive 12, and signals 28. These computer program products provide software to the computer system 1. The invention is directed to such computer program products.
  • Computer programs are stored in main memory 8 and/or secondary memory 10. Computer programs may also be received via communications interface 24. Such computer programs, when executed, enable the computer system 1 to perform the features of the present invention, as discussed herein. In particular, the computer programs, when executed, enable the processor 4 to perform the features of the present invention. Accordingly, such computer programs represent controllers of the computer system 1.
  • the software may be stored in a computer program product and loaded into computer system 1 using removable storage drive 14, hard drive 12, or communications interface 24.
  • the control logic when executed by the processor 4, causes the processor 4 to perform the functions of the invention as described herein.
  • the invention is implemented primarily in hardware using, for example, hardware components, such as application specific integrated circuits (ASICs). Implementation of the hardware state machine so as to perform the functions described herein will be apparent to persons skilled in the relevant art(s).
  • Figure 3 shows a communication system 30 of the present invention for use with the computer system 1 of Figure 2.
  • the communication system 30 includes an accessor 31 (also referred to interchangeably herein as a "user") and a terminal 32.
  • data for use in the computer system 1 is, for example, input and/or accessed by the accessor 31 via the terminal 32, such as a personal computer (PC), minicomputer, mainframe computer, microcomputer, telephonic device, or wireless device, such as a hand-held wireless device coupled to a server 33, such as a PC, minicomputer, mainframe computer, microcomputer, or other device having a processor and a repository for data and/or connection to a processor and/or repository for data, via, for example, a network 34, such as the Internet or an intranet, and couplings 35, 36.
  • the couplings 35, 36 include, for example, wired, wireless, or fiberoptic links.
  • the method and system of the present invention operate in a stand-alone environment, such as on a single terminal.
  • FIG. 3B shows a flow chart according to a method in accordance with an embodiment of the present invention.
  • a sample to be analyzed is injected into a column of a gas chromatograph along with a flowing gas via an injector.
  • the constituents of the sample are separated within the column of the gas chromatograph.
  • the constituents are moved through and out of the column with the flowing gas.
  • the constituents of the sample are divided as the constituents exit the column. The divided constituents are supplied to a flame ion detector and a mass spectrometer.
  • the sample is divided via a divider, and the constituents are heated at a temperature necessary to ensure that there is no molecule discrimination between the supply of constituents to the mass spectrometer and the supply of constituents to the flame ion detector.
  • the portion of the constituents that is sent to the mass spectrometer and the portion of the constituents that is sent to the flame ion detector are approximately equal, and the integrity of the constituents is preserved.
  • the characteristics of the constituents of the sample are detected via the flame ion detector.
  • the characteristics of the constituents of the sample are detected via the mass spectrometer.
  • steps S5 and S6 describe the detection via the mass spectrometer occurring before the detection via the flame ion detector, the order could be reversed, or the detection via both the mass spectrometer and the flame ion detector can take place at the same time.
  • the data may be acquired and processed by a data processing system. The accumulated data from both detectors obtained from continuous equal time slice analysis is stored for subsequent processing.
  • Yields and compositions in terms of the boiling point distributions and hydrocarbon type breakdowns across the boiling range of interest, may be determined.
  • changes in chemical compositions and yields in upgrading and/or conversion processes may be analyzed and studied.
  • the present invention may be used to establish a preliminary evaluation of a variety of geochemical parameters or biomarkers for the correlation to fingerprint identification, maturity, origins, etc., of crude oil or fraction thereof that is analyzed.
  • Experimental data may be correlated to chemical and physical properties. This enables refining strategies to be planned to maximize yields of required products without affecting their quality. Feedstocks can be rapidly tested by correlating the composition of products to quality.
  • the distribution and type of sulphur compounds in distillates may be determined.
  • the profile and quantities of heterocompounds in distillates may be studied by coupling specific detectors to the apparatus.
  • Figure 4 shows the multidimensionality of the information that may be gathered.
  • Figure 4 also shows the results detected by the MS, the results detected by the FID, and the combined information.
  • the present invention is fast, with high repeatability, as shown in
  • Figures 5 and 6 show the results for 3 injections, with one axis showing the signal intensity and the other showing time. The three results nearly overlap each other. The actual values for the three injections are shown in the boiling point table.
  • Figure 6 shows another set of results for three injections of paraffinic crude oil, produced using a method and system in accordance with an embodiment of the present invention.
  • the present invention can serve as an excellent screening technique to study the efficiency of physical distillations and refining processes and can rapidly establish the main compositional characteristics of crude oils, so that their quality for decision making purposes can be quickly established. Further, the present invention can serve as part of a quick exploration tool to establish the principle characteristics of crude oil quality allowing for decisions on refinement planning and commercialization.
  • Figure 7 shows a retention time standard for ASTM D 7169-2005.
  • Figure 8 shows a crude oil boiling point calibration curve.
  • Figure 9 shows the measured results of a reference material.
  • Figure 10 shows the measured results for a crude oil sample.
  • Figure 11 shows algorithms used for analyzing for each time slice the contributions of each ion characteristic of the hydrocarbon group of aromatics and saturates. Although Figure 11 references algorithms disclosed in Robinson (Analytical Chemistry, Vo. 43, 11, 1971), these algorithms are exemplary only and other, more refined algorithms and multiple variant equations may be used to extract the various compositions of the various constituents of the sample being tested. These algorithms allow the superimposition of masses at various time intervals to extract the composition of each constituent.
  • Figure 12 shows a group type analysis of compounds that may be found within crude oil.
  • Figure 13 shows a retention time calibration standard, useable according to a method and system of an embodiment of the present invention.
  • Figure 14 shows a whole crude oil analysis, produced according to a method and system of an embodiment of the present invention.
  • Figure 15 shows experimental results of a measured fraction.
  • Figure 16 shows the signal overlapping from fractions, along with crude oil.
  • Figure 17 shows an analysis of Fraction #1.
  • Figure 18 shows an analysis of fraction #1 cut in whole crude.
  • Figure 19 shows the results of a sample of paraffinic light crude oil.
  • Figure 20 shows the results of a sample of paraffinic crude oil.
  • Figure 21 shows the results for samples of lube oil fractions.
  • Figures 22 and 23 show a hydrocarbon type analysis from a whole crude sample.
  • Figure 24 shows a comparative study of middle hydrocarbon samples.
  • Figures 25-51 contain various data and other information produced using systems and methods of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

L'invention concerne un procédé et un système pour la détermination rapide d'une composition de type hydrocarbure, tel des pétroles bruts et leurs fractions et pour obtenir les informations nécessaires pour évaluer en un seul procédé le rendement de carburant et d'huile lubrifiante à valeur commerciale ; des variations du procédé et du système utilisant la chromatographie gazeuse - DIF/spectrométrie de masse et autres caractéristiques, dont un échantillonneur automatique, une colonne WCOT, un injecteur à température programmée, un système de traitement de données pour compiler et traiter les données expérimentales. Le système et la méthode comprennent en outre un système informatique avec logiciel d'application ou autre mécanisme de traitement et facultativement un réseau de communication. Une variante fournit une interface utilisateur graphique pour l'entrée de données et pour afficher les informations, par exemple sous forme graphique, pour montrer la relation qui existe entre divers résultats et données de sortie.
EP07835930A 2006-06-29 2007-06-29 Procédé et système pour la caractérisation chimique et physique d'échantillons complexes Pending EP2044613A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US81707606P 2006-06-29 2006-06-29
PCT/US2007/015131 WO2008005335A2 (fr) 2006-06-29 2007-06-29 Procédé et système pour la caractérisation chimique et physique d'échantillons complexes

Publications (2)

Publication Number Publication Date
EP2044613A2 true EP2044613A2 (fr) 2009-04-08
EP2044613A4 EP2044613A4 (fr) 2010-02-10

Family

ID=38895134

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07835930A Pending EP2044613A4 (fr) 2006-06-29 2007-06-29 Procédé et système pour la caractérisation chimique et physique d'échantillons complexes

Country Status (4)

Country Link
EP (1) EP2044613A4 (fr)
CA (1) CA2659402C (fr)
MX (1) MX2009000099A (fr)
WO (1) WO2008005335A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012012657A2 (fr) * 2010-07-21 2012-01-26 Griffin Analytical Technologies, L.L.C. Appareils d'admission d'analyse de substrat, instruments d'analyse de substrat et procédés d'analyse de substrat
CN104422745B (zh) * 2013-09-02 2016-05-11 中国石油天然气股份有限公司 用于进行样品分析的测试方法、测试装置和测试设备
CN114577966B (zh) * 2020-11-18 2023-08-08 湘潭大学 一种mscc结合调制峰归类的gc×gc指纹快速比较方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3291980A (en) * 1963-11-29 1966-12-13 Perkin Elmer Corp Combined chromatograph and mass spectrometer analyzing apparatus
EP0833155A1 (fr) * 1996-09-12 1998-04-01 Exxon Research And Engineering Company Détermination des courbes de points d'ébullition d'un pétrol brut ou d'une fraction
EP0921393A2 (fr) * 1997-12-06 1999-06-09 GSF-Forschungszentrum für Umwelt und Gesundheit GmbH Procédé à base de REMPI-TOFMS pour la détection des substances ou des classes de substances
US6354136B1 (en) * 1998-03-10 2002-03-12 Gerstal Gmbh Co., Kg Gas chromatograph with a temperature-controlled injector
US20060125826A1 (en) * 2004-12-10 2006-06-15 Lubkowitz Joaquin A Method and system for mass spectrometry and gas chromatographic data analysis
WO2007047770A2 (fr) * 2005-10-18 2007-04-26 Separation Systems Inc. Procédé et système de caractérisation chimique et physique d’échantillons complexes

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9418638D0 (en) * 1994-09-15 1994-11-02 Fisons Plc Isotopic composition analyser
US6865926B2 (en) * 2000-01-25 2005-03-15 State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of Portland State University Method and apparatus for sample analysis

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3291980A (en) * 1963-11-29 1966-12-13 Perkin Elmer Corp Combined chromatograph and mass spectrometer analyzing apparatus
EP0833155A1 (fr) * 1996-09-12 1998-04-01 Exxon Research And Engineering Company Détermination des courbes de points d'ébullition d'un pétrol brut ou d'une fraction
EP0921393A2 (fr) * 1997-12-06 1999-06-09 GSF-Forschungszentrum für Umwelt und Gesundheit GmbH Procédé à base de REMPI-TOFMS pour la détection des substances ou des classes de substances
US6354136B1 (en) * 1998-03-10 2002-03-12 Gerstal Gmbh Co., Kg Gas chromatograph with a temperature-controlled injector
US20060125826A1 (en) * 2004-12-10 2006-06-15 Lubkowitz Joaquin A Method and system for mass spectrometry and gas chromatographic data analysis
WO2007047770A2 (fr) * 2005-10-18 2007-04-26 Separation Systems Inc. Procédé et système de caractérisation chimique et physique d’échantillons complexes

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
NITZ S; DRAWERT F, GELLERT U: "A Variable Effluent Splitter for Simultaneous Sniffing-MS-Monitoring" CHROMATOGRAPHIA, vol. 22, no. 1-6, June 1986 (1986-06), pages 51-54, XP002561130 VIEWEG&SOHN VERLAG *
OHBA T ET AL: "DECOMPOSITION PROPERTY OF METHYLHYDRAZINE WITH TITANIUM NITRIDATIONLOW TEMPERATURE" JOURNAL OF THE ELECTROCHEMICAL SOCIETY, ELECTROCHEMICAL SOCIETY. MANCHESTER, NEW HAMPSHIRE, US, vol. 142, no. 3, 1 March 1995 (1995-03-01), pages 934-938, XP000504900 ISSN: 0013-4651 *
See also references of WO2008005335A2 *

Also Published As

Publication number Publication date
WO2008005335A2 (fr) 2008-01-10
EP2044613A4 (fr) 2010-02-10
CA2659402A1 (fr) 2008-01-10
MX2009000099A (es) 2009-02-13
CA2659402C (fr) 2015-02-03
WO2008005335A3 (fr) 2008-07-03

Similar Documents

Publication Publication Date Title
US8413484B2 (en) Method and system for chemical and physical characterization of complex samples
US7509837B2 (en) Method and system for chemical and physical characterization of complex samples
CN107709983B (zh) 使用真空紫外光谱和气相色谱对复杂样品进行详细的批量分类分析的方法
AU696178B2 (en) Method for predicting chemical or physical properties of crude oils
EP0833878B1 (fr) Procede de preparation d'huiles lubrifiantes
EP0871976B1 (fr) Procede de preparation de produits melanges
US6183635B1 (en) Hydrocarbon class separation and quantitation by split column effluent analysis
EP0833155B1 (fr) Détermination des courbes de points d'ébullition d'un pétrol brut ou d'une fraction
EP3060906B1 (fr) Analyse d'hydrocarbure intégrée
US20060125826A1 (en) Method and system for mass spectrometry and gas chromatographic data analysis
US7619212B2 (en) Chromatographic analyzer
Coutinho et al. Understanding the molecular composition of petroleum and its distillation cuts
CA2659402C (fr) Procede et systeme pour la caracterisation chimique et physique d'echantillons complexes
Wang GC× VUV study of diesel: A two-dimensional separation approach
Hsu et al. Molecular characterization of diesel fuels using modern analytical techniques
US5644129A (en) Direct analysis of paraffin and naphthene types in hydrocarbon
US6492639B1 (en) Method and apparatus for recognizing properties of a sample based on mass spectroscopy
EP0444946A2 (fr) Procédé de mesure quantitative des oléfines saturées et aromatique dans un mélange
KR20210059169A (ko) 다성분 혼합물의 동시 분석을 위한 방법 및 시스템
CN113804533A (zh) 作为关于进一步分离的肯定或否定决定的基础的分离的样品部分的纯度检测
Bell et al. Limits of identification using VUV spectroscopy applied to C8H18 isomers isolated by GC× GC
JP2006023184A (ja) 軽油の分析方法
Mendez et al. Physical and chemical characterization of petroleum products by GC-MS
Geddes et al. Semi‐automated tandem mass spectrometric (MS/MS) triple quadrupole operating parameter optimization for high‐throughput MS/MS detection workflows
Baldrich et al. Development of a methodology to determine the aromatic structural distribution in light and medium petroleum fractions by HPLC

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090128

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

DAX Request for extension of the european patent (deleted)
RIC1 Information provided on ipc code assigned before grant

Ipc: G01N 30/72 20060101ALI20091228BHEP

Ipc: G01N 30/68 20060101ALI20091228BHEP

Ipc: G01N 30/10 20060101AFI20091228BHEP

A4 Supplementary search report drawn up and despatched

Effective date: 20100111

17Q First examination report despatched

Effective date: 20100426

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS