WO2012104858A1 - Procédé d'analyse en ligne pour pétroles bruts faisant appel à la spectroscopie - Google Patents

Procédé d'analyse en ligne pour pétroles bruts faisant appel à la spectroscopie Download PDF

Info

Publication number
WO2012104858A1
WO2012104858A1 PCT/IN2011/000222 IN2011000222W WO2012104858A1 WO 2012104858 A1 WO2012104858 A1 WO 2012104858A1 IN 2011000222 W IN2011000222 W IN 2011000222W WO 2012104858 A1 WO2012104858 A1 WO 2012104858A1
Authority
WO
WIPO (PCT)
Prior art keywords
sample
crude oil
solvent
absorption
crude
Prior art date
Application number
PCT/IN2011/000222
Other languages
English (en)
Inventor
Bisht HARENDER
Preschilla NISHA
Saravanan CHANDRA
Mandal SUKUMAR
Das ASIT
Original Assignee
Reliance Industries Ltd.
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 Reliance Industries Ltd. filed Critical Reliance Industries Ltd.
Publication of WO2012104858A1 publication Critical patent/WO2012104858A1/fr

Links

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
    • G01N33/2823—Raw oil, drilling fluid or polyphasic mixtures
    • 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

Definitions

  • the present invention relates to simple and accurate method for online analysis of oil samples.
  • the invention relates to an improved method for online IR analysis of cirude oil by diluting the crude oil with IR transparent solvent.
  • a major problem in evaluating crude oil through online analysis method of the state of art is high viscosity of the crude oil which makes it difficult to flow through the online sample cell for accurate analysis.
  • Another major difficulty, particularly in the mid IR analysis, is the complete absorption of IR radiation in the region 2800 to 3100cm “1 and 1100 to 1400 cm “1 . Due to complete absorption no useful information can be retrieved from these regions ( Figure 1).
  • US6662116 B2 teaches to determine the properties of unknown materials by IR analysis. However, this patent does not teach how to analyze the crude oil online.
  • US3996785 describes measurement of boiling point properties of crude by help of IR analysis, kinematic viscosity measurement and S analysis. This patent uses data from multiple sources to predict the boiling point properties of crude oil.
  • WO2008135411A1 describes IR analysis method in batch mode using ATR technique. However, it does not indicate any dilution of crude oil and any corresponding online system for that.
  • US6087662 discloses an online process for determining asphaltene concentration in an asphaltene-containing hydrocarbon mixture using infrared spectroscopy and a multiple variable regression analysis.
  • the Asphaltene content is predicted by Mid IR analysis using NaCl plates and Tunnel ATR cell in batch manner.
  • Employing this method to an online and continuous system is seemingly non-feasible. Therefore, the proposed invention is distinct from the said process.
  • JP58037543A discloses a method for performing quantitative analysis by an infrared spectrophotometry to measure the amount of a curing agent in an epoxy resin using 0.05mmKBr cell and diluting the sample with chloroform (CHC1 3 ).
  • An object of present invention is to provide an improved method for accurate analysis of crude oil for determining several physico-chemical properties of crude oil in real time.
  • Another object of the invention is to reduce the viscosity of the crude oil in order to allow better flow through the IR sample cell.
  • Another object of the invention is to perform IR analysis of crude oil using smaller IR sample cell than a typical IR sample cell.
  • Still another object of the invention is to utilize full IR spectrum from 4000 cm “1 to 400 cm “1 for predicting the properties of crude under examination by adding an inert solvent, particularly Carbon tetrachloride.
  • Still another object of the invention is to perform contamination free analysis by making the IR sample cell free of any residual crude oil with little cleaning effort.
  • Yet another object of the invention is to use Carbon tetrachloride as cleaning solution for IR sample cell in order to quickly clean the cell.
  • an improved method for online IR analysis of crude oil wherein, the crude oil is diluted with CC1 4 and the IR analysis of this diluted crude solution is done online.
  • the said method Comprises the steps of:
  • Figure 1 shows the graphical representation of wave numbers on X-axis along with IR absorbance on Y-axis in the prior art in which the region 2800 to 3200cm “1 (C-H stretching vibrations) and 1100 to 1500 cm “1 is completely opaque to IR radiation and no information can be retrieved from these regions for as such crude samples (US6662116 B2);
  • FIG. 2 shows that Carbon tetra chloride (CC1 4 ) is almost transparent to IR radiation except 750 to 800 cm "1 region;
  • Figure 3 shows the IR spectra of pure crude vis a vis crude diluted with CC14 in ATR mode
  • Figure 4 shows the IR spectra of pure and CC1 4 diluted crude in 0.05mm KBr cell
  • Figure 5 shows the difference in absorption intensity of pure and CC14 dilutes crude in 2800 - 3100 cm "1 band in 0.05mm KBr cell.
  • the present invention provides an improved method for online IR analysis of crude oil, wherein, the dilution of crude oil is done with IR transparent solvent, particularly Carbon tetrachloride and the IR analysis of this diluted crude solution is done online.
  • the said method comprises the steps of:
  • IR sample cells typically have a path length in the range of 0.2mm - 0.5 mm. Even at the lower limit of path length i.e. 0.2mm, two regions i.e. 2800-3100 cm “1 and 1100- 1500 cm “1 ) show 100% absorption of IR radiation (US patent 6662116 B2), due to which, no information can be retrieved from these regions for as such crude samples. There is no state of art method available, wherein, an online sample cell of 0.05 mm path length is used.
  • IR sample cells with smaller path length could not be used due to following two reasons:
  • solvents selected from the group consisting of halogenated CI to C 3 hydrocarbons including l,2-dibromo-l,l,2,2-tetrachloroethane (C 2 Br 2 Cl 4 ) and Hexachloroethane (C 2 C1 6 ) can also be used. Similar to carbon tetrachloride solution, these two solvents l,2-dibromo-l,l,2,2-tetrachloroethane and Hexachloroethane are also transparent to the region of interest of IR radiation except at 600 cm "1 to 800 cm “1 .
  • Crude oil diluted in CC1 is found to have considerably lower viscosity and it can smoothly flow through the online IR sample cell.
  • the absorption intensity is significantly lower for the diluted crude oil so more information can be retrieved from the 2800 to 3100 cm “1 (CH stretching) and 1100 to 1500 cm “1 (CH bending) region, which was never hitherto possible for pure crude oil.
  • the present invention therefore provides a solution to the longstanding problem of crude oil analysis by providing the following improvements:
  • the viscosity of diluted crude solution is significantly reduced therefore the flow of sample through the online cell is much easier as compared to the pure crude oil.
  • sample cells of less than 0.2mm e.g. 0.05mm
  • the absorbance intensity of crude oil in regions 2800 cm “1 -3100 cm “1 and 1100 cm “1 -1500cm "1 is reduced considerably therefore full IR spectrum from 4000 cm “1 to 400 cm “1 is used for predicting the properties of crude under examination.
  • the cleaning of the cell is better therefore the analysis is more accurate and contamination of online IR cell with previously analyzed crude sample is minimized.
  • Figure 3 shows the IR spectra of pure crude vis a vis crude diluted with CC14 in ATR mode.
  • the red line represents the IR absorption by pure crude and the brown line represents the IR absorption by 9 % crude in CC1 4 ( Figure 3).
  • the IR absorption intensity in 2800 cm “1 - 3100 cm “1 and 1100cm “1 - 1500cm "1 ranges has decreased by >50% and >85% for 9% crude in CC1 4 respectively.
  • Figure 4 shows the IR spectra of pure and CC1 4 diluted crude in 0.05mm KBr cell.
  • the absorbance band at 2800-3100 cm “1 is fully saturated (100% absorbance) and the band at 1400 - 1450 cm “1 is also approaching saturation (-100% absorbance). Since it is not , possible to determine the decrease in absorption by 0.05 mm KBr cell, the decrease was estimated from the ATR measurement.
  • Figure 5 shows the difference in absorption intensity of pure and CC1 4 diluted crude in 2800- 3100 cm "1 band in 0.05mm KBr cell. It is clearly evident that no information can be retrieved from the IR spectra of pure crude due to 100% absorbance whereas, the diluted crude shows distinct peak patterns with 50 to 91%dilutions.
  • the reduction in absorbance with dilution using the method in accordance with this invention is tabulated in Table No. 1 and Table No. 2.
  • the diluted crude solution prepared in accordance with the method of the invention was examined under optical microscope to check if there is sedimentation or precipitation of CC1 4 insoluble components.
  • the optical microscope images showed no aggregates and/or precipitates with 50 to 91% dilution of crude oil by CC1 4 . Therefore the homogeneity of crude oil is maintained after dilution with CC1 4 .
  • Contamination free analysis can be performed by making the IR sample cell free of any residual crude oil with little cleaning effort.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Analytical Chemistry (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

L'invention concerne un procédé amélioré pour une analyse IR en ligne de mélange d'hydrocarbures, en particulier de pétroles bruts, pour déterminer leurs propriétés physico-chimiques; un échantillon de pétrole étant dilué avec un solvant laissant passer les rayons IR, en particulier du tétrachlorure de carbone et une absorption des rayons IR étant évaluée. L'invention met en oeuvre un procédé dans lequel des cellules d'échantillon de moins de 0,2 mm peuvent être utilisées et un spectre IR complet de 800 cm-1 à 400 cm-1 peut être utilisé pour prédire les propriétés du pétrole.
PCT/IN2011/000222 2011-02-01 2011-03-30 Procédé d'analyse en ligne pour pétroles bruts faisant appel à la spectroscopie WO2012104858A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN276MU2011 2011-02-01
IN276/MUM/2011 2011-02-01

Publications (1)

Publication Number Publication Date
WO2012104858A1 true WO2012104858A1 (fr) 2012-08-09

Family

ID=46602141

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2011/000222 WO2012104858A1 (fr) 2011-02-01 2011-03-30 Procédé d'analyse en ligne pour pétroles bruts faisant appel à la spectroscopie

Country Status (1)

Country Link
WO (1) WO2012104858A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3071321A4 (fr) * 2013-11-18 2017-06-07 Indian Institute Of Technology Madras Systèmes et procédés pour sélectionner des solvants pour dissoudre des boues de fond de réservoir

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050279131A1 (en) * 2004-06-16 2005-12-22 Battiste David R Noninvasive measurement and control system for use in hydrocarbon processing
CN101487818A (zh) * 2009-02-20 2009-07-22 国网电力科学研究院 变压器油中气体含量在线监测方法及系统
CN101846628A (zh) * 2009-03-27 2010-09-29 上海神开石油化工装备股份有限公司 钻井液的在线拉曼光谱分析方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050279131A1 (en) * 2004-06-16 2005-12-22 Battiste David R Noninvasive measurement and control system for use in hydrocarbon processing
CN101487818A (zh) * 2009-02-20 2009-07-22 国网电力科学研究院 变压器油中气体含量在线监测方法及系统
CN101846628A (zh) * 2009-03-27 2010-09-29 上海神开石油化工装备股份有限公司 钻井液的在线拉曼光谱分析方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3071321A4 (fr) * 2013-11-18 2017-06-07 Indian Institute Of Technology Madras Systèmes et procédés pour sélectionner des solvants pour dissoudre des boues de fond de réservoir

Similar Documents

Publication Publication Date Title
ES2731891T3 (es) Método para predecir la estabilidad de corrientes de proceso de hidrocarburos usando espectros de infrarrojo cercano
Tian et al. Classification of wines according to their production regions with the contained trace elements using laser-induced breakdown spectroscopy
Chung et al. Comparison of near-infrared, infrared, and Raman spectroscopy for the analysis of heavy petroleum products
US7067811B2 (en) NIR spectroscopy method for analyzing chemical process components
Abbas et al. PLS regression on spectroscopic data for the prediction of crude oil quality: API gravity and aliphatic/aromatic ratio
Harvey et al. Blind field test evaluation of Raman spectroscopy as a forensic tool
Dearing et al. Characterization of crude oil products using data fusion of process Raman, infrared, and nuclear magnetic resonance (NMR) spectra
CA2990022C (fr) Procede et dispositif de determination d'une propriete d'un materiau bitumineux
Brunnbauer et al. Combined LA-ICP-MS/LIBS: powerful analytical tools for the investigation of polymer alteration after treatment under corrosive conditions
Li et al. Nondestructive detection of lead chrome green in tea by Raman spectroscopy
Cui et al. Excitation emission matrix fluorescence spectroscopy and parallel factor framework-clustering analysis for oil pollutants identification
Yu et al. Response surface methodology for optimizing LIBS testing parameters: A case to conduct the elemental contents analysis in soil
Uriarte et al. The self-absorption phenomenon in quantitative Raman spectroscopy and how to correct its effects
WO2012104859A1 (fr) Appareil d'analyse en ligne de fluides visqueux par spectroscopie
Ruiz et al. A multivariate calibration approach for determination of petroleum hydrocarbons in water by means of IR spectroscopy
WO2012104858A1 (fr) Procédé d'analyse en ligne pour pétroles bruts faisant appel à la spectroscopie
Abbas et al. Prediction of source rock origin by chemometric analysis of Fourier transform infrared–attenuated total reflectance spectra of oil petroleum: evaluation of aliphatic and aromatic fractions by self-modeling mixture analysis
Tellez et al. Comparison of purge and trap GC/MS and spectrophotometry for monitoring petroleum hydrocarbon degradation in oilfield produced waters
Burley et al. Quantification of pharmaceuticals via transmission Raman spectroscopy: data sub-selection
Musso et al. Analysis of the Brill transition and reversible brill transition in nylon 6, 6 by Raman spectroscopy
Luna et al. Rapid assessment of total and polycyclic aromatic contents in heavy oils
Huang et al. Trace PFAS Detection in Water Sources Using Silver Nanoparticles for Surface-Enhanced Raman Spectroscopy (SERS)
Benhabib et al. Surface-Enhanced Raman Spectroscopy for Rapid and Cost-Effective Quantification of Amines in Sour Water
Macián et al. Application assessment of UV–vis and NIR spectroscopy for the quantification of fuel dilution problems on used engine oils
CN114088686B (zh) 一种实时无损测定氯化石蜡中氯含量的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11857792

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11857792

Country of ref document: EP

Kind code of ref document: A1