Quantitative Determination of Asphaltenes and Resins in Solution by Means of Near-Infrared Spectroscopy. Correlations to Emulsion Stability

Kallevik, Harald; Kvalheim, Olav M.; Sjöblom, Johan

doi:10.1006/jcis.2000.6764

Cited by 46 publications

(25 citation statements)

References 18 publications

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“…Blanco et al (2000Blanco et al ( , 2001 used a scanning-grating NIR spectro-scope (NIRSystems 6500) in the wavelength range of 1100 to 2500 nm with a sample cuvette of 0.2 mm light path length to determine the penetration value, viscosity, density, softening point, Fraass breaking point, and SARA (saturates, aromatics, resins, and asphaltenes) composition of "bitumen" -the heavy crude oil fraction obtained by direct distillation. Kallevik et al (2000) used the same NIR instrument to analyze asphaltene and resin concentrations in solvent-diluted asphalteneresin solutions. Friesen (1996) used the NIRSystem 6500 instrument with a diffuse reflectance probe for qualitative analysis of oil sands slurries.…”

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confidence: 99%

Analysis of Solvent‐Diluted Bitumen from Oil Sands Froth Treatment Using NIR Spectroscopy

2004

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I n the extraction of bitumen from oil sands, bitumen froth treatment is an essential step to remove water and solids from bitumen froth (Clark and Pasternack, 1932;Tipman and Shaw, 1993). The bitumen froth usually contains about 60 wt% bitumen, 30 wt% water, and 10 wt% solids. Current commercial froth treatment employs naphtha dilution followed by multistage centrifugation, which gives a diluted bitumen product containing 0.3 to 1.0 wt% solids and 1 to 5 wt% water (Tipman and Shaw, 1993). An alternative froth treatment process that uses aliphatic solvent as diluent can produce a diluted bitumen product that contains less than 0.1 wt% water/solids and controlled levels of asphaltenes (Long et al., 2002(Long et al., , 2004Tipman and Long, 1999;Tipman et al., 2001). The performance of bitumen froth treatment process using aliphatic solvent depends greatly on controlling process parameters; among the most important of these are the solvent-to-bitumen ratio (S/B, by wt), asphaltenes rejection level, and density of the solventdiluted bitumen oil phase. Successful control of these process parameters ensures the desired level of asphaltenes in product, sufficiently high settling flux of water and solids, and on-spec product (e.g., containing less than 0.1 wt% water-plus-solids).At present, the S/B of solvent-diluted bitumen is usually determined by vacuum rotary evaporation (Rotavapor), the asphaltenes content in bitumen is analyzed using the standard ASTM (ASTM D 3279-97) or IP (IP 143-96) methods based on precipitation of asphaltenes by light aliphatic solvent followed by filtration, and the density of solvent-diluted bitumen is measured using a laboratory density meter. These analyses are labourintensive and time-consuming. Rotavapor takes approximately 1.5 h to complete and asphaltene content analysis takes about 6 h. Furthermore, the accuracy of the analytical results is subjected to the skill of the analyst. Consistency of the results from various laboratories is frequently not s a t i s f a c t o ry. Therefore, more reliable and faster analytical methods are required to better monitor performance and to permit timely adjustments of the operating conditions for bitumen froth treatment.Near-infrared (NIR) spectroscopy provides information on chemical and physical properties of sample components. Chemometric methods based on eigenvalue decomposition of a data matrix are effective tools for analyzing correlations between spectral information and sample composition and properties (Beebe and Kowalski, 1987;Kramer, 1998). NIR spectroscopy in combination with chemometrics is hence a powerf u l approach for convenient routine laboratory and on-line analysis.NIR techniques that have found applications in petroleum industry include determination of gasoline properties e.g. octane number, vapour * Author to whom correspondence may be addressed. E-mail address: ylong@nrcan.gc.caProcess control and optimization of bitumen froth treatment during oil sands processing require rapid analysis of asphaltene content in bitumen, solve...

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Analysis of Solvent‐Diluted Bitumen from Oil Sands Froth Treatment Using NIR Spectroscopy

2004

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“…This degree of resolution approaches that of gas chromatography, which is often accepted as the laboratory gold standard with reported accuracies only 2 to 5 times greater. These studies all demonstrate that a high resolution chemometric dot product regression applied to information-rich, broad-range, high-resolution spectroscopic data yields measurements that approach a laboratory gold standard (Macho et al1999;Kallevik et al 2000;Aske et al 2001;Satya et al 2007). …”

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confidence: 93%

“…For absorption spectroscopy, a wealth of fingerprint information may be derived in the near-and mid-infrared vibration absorption regions (Mattson et al 1977). Multiple authors (Mattson 1977, Khadmin 1999, Macho 1999, Kallevik 2000, Aske 2001, Aske 2002, Satya 2006) have used high-resolution dot product regression of high-resolution optical data to provide chemometric prediction of oil fractions and properties, including saturates, aromatics, resins, and asphaltenes fractions, density, and molecular weight. Relative model uncertainties are typically in the range of the range of 1 to 4%, depending on the study and parameter.…”

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Laboratory Quality Optical Analysis in Harsh Environments

et al. 2012

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Significant advances have been made in formation testing since the introduction of wireline pumpout testers (WLPT), particularly with respect to downhole fluid compositional measurements. Optical sensors and the use of spectroscopic methods have been developed to improve sample quality and minimize sampling time in downhole environments. As a laboratory technique, spectroscopy is a ubiquitous and powerful technology that has been used worldwide for decades to measure the physical and chemical properties of many materials, including petroleum, geological, and hydrological samples. However, laboratory-grade, high-resolution spectrometers are incompatible with the hostile environments encountered downhole, at wellheads, and on pipelines. Only limited resolution techniques are available for the rugged conditions of the oil field. This paper introduces a new optical technology that can provide high-resolution, laboratory-quality analyses in harsh oilfield environments.A new technology for optical sensing, multivariate optical computing (MOC), has been developed and is a nonspectroscopic technique. This new sensing method uses an integrated computation element (ICE) to combine the power and accuracy of high-resolution, laboratory-quality spectrometers with the ruggedness and simplicity of photometers. Many modern sensors typically merge the sensor with the electronics on an integrated computing chip to perform complex computations, resulting in an elegant yet simplistic design. Now, optical sensing using ICE features an analogue optical computation device to provide a direct, simple, and powerful mathematical computation on the optical information, completely within the optical domain. Because the entire optical range of interest is used without dispersing the light spectrum, the measurements are obtained instantly and rival laboratory-quality results.A proof of concept MOC with ICE has been demonstrated, logging more than 7,000 hours, in nearly continuous use for 14 months. Oils with gravities ranging from 14 to 65°API have been measured in downhole environments that range from 3,000 to 20,000 psi, and from 150 to 350°F. Hydrocarbon composition measurements, including saturates, aromatics, resins, asphaltenes, methane, and ethane, have been demonstrated using the MOC configuration. As compositional calculations therein, GOR and density are validated to within 14 scf/bbl and 1%, respectively. The paper discusses the details of the new ICE-based sensor and describes its adaptations to downhole applications.

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“…2,3 In this point, the chemometrics, associated with spectroscopy (near and midinfrared in particular), has shown potential as a tool for analytical chemistry by generating alternative methods for the characterization and evaluation of physical and chemical properties of petroleum and its derivatives with high precision, reliability and speed. [4][5][6][7][8][9][10] Such methods have increasingly been used in petroleum and its derivatives data, since these products are generally highly complex, and their physicochemical characterization requires considerable effort. In this context, sometimes there is urgency to obtain results of certain analysis and the decision-making is hampered by the way the analyses are made.…”

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Sulfur Determination in Brazilian Petroleum Fractions by Mid-infrared and Near-infrared Spectroscopy and Partial Least Squares Associated with Variable Selection Methods

et al. 2016

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Chemometric tools (PLS) with variable selection (iPLS, siPLS, UVE and GA), associated with near infrared (NIR) and mid infrared (MIR) spectroscopy, were applied for the determination of sulfur content (wt %) in petroleum derivatives. The evaluation of the models was conducted by the determination and analysis of the following requirements: coefficient of determination (R 2 ); the curve obtained by plotting the predicted versus measured values; and also the cross-validation and prediction errors.The developed models presented in this work had satisfactory results, demonstrating that both NIR and MIR techniques, combined with chemometric tools, can be used to determine the sulfur content in petroleum fractions, with LOD and LOQ from 0.0234 and 0.0781 respectively. All variable selection techniques improved the predictive ability of the mode when compared with the full-spectra model, except the UVE method that showed a better performance only when associated with MIR data.

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Quantitative Determination of Asphaltenes and Resins in Solution by Means of Near-Infrared Spectroscopy. Correlations to Emulsion Stability

Cited by 46 publications

References 18 publications

Analysis of Solvent‐Diluted Bitumen from Oil Sands Froth Treatment Using NIR Spectroscopy

Analysis of Solvent‐Diluted Bitumen from Oil Sands Froth Treatment Using NIR Spectroscopy

Laboratory Quality Optical Analysis in Harsh Environments

Sulfur Determination in Brazilian Petroleum Fractions by Mid-infrared and Near-infrared Spectroscopy and Partial Least Squares Associated with Variable Selection Methods

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