Applications of Near‐Infrared Spectroscopy in Refineries and Important Issues to Address

Abstract

This review primarily concerns NIR (near‐infrared) applications in refineries. Initially, this article reviews the fundamental aspects for analysis of hydrocarbon mixture by NIR spectroscopy, such as spectral sensitivity in various spectral regions, signal‐to‐noise ratio, and spectral resolution. Though there are applications of NIR to diverse petroleum products, this review subsequently focuses only on applications to four major products: gasoline, diesel, naphtha, and crude oil, which are the most interesting from a refiner's viewpoint. In each application, discussion of important issues to consider for proper and optimal NIR measurement is included. Finally, the issue of calibration transfer is discussed.     

Use of Multivariate Curve Resolution to Monitor an Esterification Reaction by Near‐Infrared Spectroscopy

Multivariate curve resolution–alternating least squares (MCR‐ALS) methodology was applied to near‐infrared (NIR) spectra with view to estimating the reaction profile for the esterification of a mixture of caprylic and capric acids with glycerol. The reaction was conducted in excess glycerol, so the major products were the monoglyceride and diglyceride; the triglyceride was obtained in considerably lower proportions. Esterification processes were performed in a laboratory‐scale reactor from which samples were withdrawn to record NIR spectra. Some samples were also analyzed by gas chromatography and acid‐base titration in order to determine the composition of the reaction mixture. Concentration and spectral profiles were obtained by using the MCR‐ALS algorithm. Subsequently, concentration values and the pure spectra of reagents and the triglyceride were used to refine the models. The spectra obtained were processed with MCR‐ALS in new esterification batches to obtain their concentration profiles.     

Quantitatively Determination of Available Phosphorus and Available Potassium in Soil by Near Infrared Spectroscopy Combining with Recursive Partial Least SquaresSCIEI北大核心CSCD

Soil available phosphorus (P) and available potassium (K) don't possess direct spectral response in the near infrared (NIR) region. They are predictable because of their correlation with spectrally active constituents (organic matter, carbonates, clays, water, etc.). Such correlation may of course differ between the soil sample sets. Therefore, the NIR calibration models with fixed structure are difficult to achieve good prediction performances for soil P and K. In this work, the method of recursive partial least squares (RPLS), which is able to update the model coefficients recursively during the prediction process, has been applied to improve the predictive abilities of calibration models. This work compared the performance of partial least squares regression (PLS), locally weighted PLS (LW-PLS), moving window LW-PLS (LW-PLS2) and RPLS for the measurement of soil P and K. The entire data set of 194 soil samples was split into calibration set and prediction set based on soil types. The calibration set was composed of 120 Anthrosols samples, while the prediction set included 29 Ferralsols samples, 23 Anthrosols samples and 22 Primarosols samples. The best prediction results were obtained by the RPLS model. The coefficient of determination (122) and residual prediction deviation (RPD) were respectively 0.61, 0.76 and 1.60, 2.05 for soil P and K. The results indicate that RPLS is able to learn the information from the latest modeling sample by recursively updating the model coefficients. The proposed method RPLS has the advantages of wider applicability and better performance for MR prediction of soil P and K compared with other methods in this work.     

Fourier‐Transform Near‐Infrared Spectroscopy as a Tool for Olive Fruit Classification and Quantitative Analysis

Abstract

The potential of diffuse reflectance near‐infrared spectroscopy combined with pattern recognition to discriminate between olives (Olea europaea L.) of different qualities has been tested. The sample set was formed of sound olive fruits and those showing the most common alterations of olives, which lead to decreased oil quality, namely freeze damages, harvest after falling on the ground, fermentation due to prolonged storage time, and olive tree diseases. Near‐infrared (NIR) spectra were recorded between 9900 and 4100 cm^?1. Preliminary studies of the data set structure were performed using hierarchical cluster analysis and principal component analysis. Discriminant analysis provided prediction abilities of 100% for sound, 79% for frostbite, 96% for ground, and 92% for fermented olives using a leave‐a‐fourth‐out cross‐validation procedure. Quantification of oil and water content in the olives was also approached by using partial least squares (PLS) regression. Results, in terms of predictive ability using a leave‐one‐out cross‐validation, were compared for calibration using the whole sample set and calibrations for the sound and damaged samples separately. Relative errors of prediction using all samples were 7.2% and 3.4% for oil content and humidity, respectively. Using only sound samples, relative errors of prediction of 3.8% and 2.8% for oil and water content, respectively, were obtained. Thus, better accuracy could be achieved when classification of the olive samples prior to quantitative analysis was performed. These results demonstrate the utility of NIR spectroscopy to differentiate olives of different qualities. Using NIR, a fast selection of sound olives in a quality‐orientated production facility becomes feasible.     

Intumescent Flame Retardancy and Thermal Degradation of Epoxy Resin Filled with Ammonium Polyphosphate Using Thermogravimetric Analysis–Fourier Transform Infrared Spectroscopy and Thermogravimetric Analysis–Mass Spectrometry

The flammability of epoxy resin (EP) and its composite with ammonium polyphosphate (EPAPP) was investigated with limiting oxygen index (LOI), UL 94, and cone calorimeter tests. A systematic and comparative evaluation of the thermal degradation of EP and EPAPP has been investigated using thermogravimetry coupled with Fourier transform infrared spectroscopy (TG–FTIR) and thermogravimetry coupled with mass spectrometry (TG–MS). The results showed that the flame retardant of ammonium polyphosphate (APP) can constitute an intumescent flame retardant (IFR) system with EP, and APP can effectively improve the LOI of EP; with 6 wt% addition level of APP, EPAPP can pass UL 94 V 0 test. The cone calorimeter test results showed that the flame retardancy and smoke suppression of EP were significantly improved by APP, and toxic gas products such as carbon monoxide and carbon dioxide obviously decreased. Thermogravimetry–Fourier transform infrared spectroscopy and TG–MS results showed that the degradation process of EP produces large amounts of gas products and mainly containing of water, carbon dioxide, methane, benzene and its derivatives, as well as phenol and its derivatives. Compared to EP, the kinds of decomposition products of EPAPP sample were not changed significantly, except that more ammonia gas was generated. For the EPAPP sample, the products of water, benzene, and phenol increased, whereas the carbon dioxide and the flammable hydrocarbon fragments C_xH_y decreased significantly during the decomposition.     

Optical and Photoluminescent Properties of Thin-Film ZnO–PLZT Structure in the UV and Visible Spectral Regions

Optics and Spectroscopy - The structural, optical, and photoluminescent properties of the thin-film structure ZnO–PLZT ferroelectric ceramics are studied. The results of X-ray diffraction...     

Mid‐ and Near‐Infrared Spectroscopic Determination of Carbon in a Diverse Set of Soils from the Brazilian National Soil Collection

Abstract

Calibrations for soil carbon content measured by combustion (total carbon, TC) and chromate oxidation by a modified Walkley‐Black method (Walkley‐Black carbon, WBC) from the Brazilian National Soil Collection were made using Fourier‐transform near (1100 to 2500 nm; NIRS) and mid‐infrared diffuse reflectance (2,500 to 25,000 nm; DRIFTS) spectroscopy combined with partial least squares (PLS). Calibration sets of sample populations of different carbon ranges, soil taxonomic classes, and soil textural groups were established. These are for TC ranges between 0.4 to 555.0, 0.4 to 99.1, and 0.4 to 39.9 g kg^?1: for WBC 0.2 to 401.0, 0.2 to 66.0, and 0.2 to 66.0, and 0.2 to 30.0 g kg^?1: for soil taxonomic classes Ferralsols and Acrisols; and for soil textural groups very clayey, clayey, and medium textures were examined. Calibrations obtained for the largest TC and WBC ranges were better compared to the lower ones, but lower root mean squared deviation (RMSD) and relative difference (RD=RMSD/mean value) were found for the lower carbon ranges. Taxonomic soil class was not an adequate criterium for calibration set formation. Soil texture had effect on calibrations, especially using NIR, because of the particle size effect to which NIR was more sensitive than mid‐IR. In general, DRIFTS showed better performance than NIRS. NIRS only outperformed DRIFTS when used with calibration set fairly homogeneous in its particle size distribution. Results demonstrated that while calibrations can be developed using either DRIFTS or NIRS for even a very diverse set of soil samples, which will determine C over a wide range of concentrations inherent in such a diverse set, it is desirable to seperate sample populations by soil textural properties and choose the adequate spectral range (NIR or mid‐IR) based on the textural group, for calibration development to achieve more accurate results.     

The Heterogeneous Mineral Content of Bone—Using Stochastic Arguments and Simulations to Overcome Experimental Limitations

On a sub-millimeter length scale, bone is a very heterogeneous material with varying mineral content. This heterogeneity can be measured by quantitative backscattered electron imaging (qBEI) and quantified by a probability distribution called the bone mineralization density distribution (BMDD). The stochastic nature of the backscattering of electrons during the measurement makes the results dependent on the acquisition time. In this work the influence of the measurement conditions was quantified and was corrected for using Tikhonov regularization. Deconvolution reduces the width of the BMDD and allows a more precise definition of a reference BMDD for healthy adults. The corrected information was used as input for a mathematical model that predicts the time evolution of the BMDD. Simulations of osteoporosis treatment reveal a double peak in the BMDD that is not observed in experiments due to limited acquisition time. Our method allows determining the necessary acquisition time to resolve such double peaks.     

Optical Observation of Lung Cancer With Attenuated Total Reflectance–Fourier Transform Infrared Microscope (ATR-FTIR) and Confocal Raman Microscope

ABSTRACT

Optical observation of lung cancer tissues using attenuated total reflectance–Fourier transform infrared microscope (ATR-FTIR) and confocal Raman microscope were performed. A total of six malignant tissues, seven tissues adjacent to cancer, and nine normal tissues from nine patients with known lung cancer were studied. High-quality spectra from human tissues were obtained only in a few seconds. The results revealed that some of the spectral characteristics varied significantly between normal and malignant tissues, that is, IR peak positions, Raman shift, and the spectral intensities. Differences in positions of 10 main peaks in IR shifts and 13 main peaks in Raman shifts were listed, and the intensity changes were also studied between the malignant and normal tissues. The ratios of 1453-cm^?1/1645-cm^?1 intensity in IR spectrum and 1245-cm^?1/1571-cm^?1 intensity in Raman spectrum were found with the most significant difference (p < 0.0001 and p < 0.05 separately) in statistics and may be used in combination to differentiate the normal and malignant tissues. ATR-FTIR spectrum and Raman spectrum were mutually complementary in the observation of many materials and were both found with high sensitivities and spatial resolutions in the observation of human tissues. This study will be helpful to developing rapid and accurate cancer detection techniques in future clinical diagnosis.     

Determination of the Heat of Adsorption and Desorption of a Volatile Organic Compound Under Dynamic Conditions Using Fourier‐Transform Infrared Spectroscopy

Quantitative Fourier‐transform infrared spectroscopic analysis was used for the determination of adsorption capacity of a model volatile organic compound (VOC) under dynamic conditions. The analytical method used also offers the possibility of distinguishing between reversible and irreversible adsorption as well as further detection of adsorbed VOC transformation. The obtained adsorbed amounts have been used for the determination of the heat of adsorption and the activation energy of desorption using, respectively, isosteric and temperature programmed desorption methods. The approach has been applied to explore the potential use of local clay as an adsorbent material for VOC pollutants.     

Smooth and Peaked Solitary Wave Solutions of the Broer–Kaup System Using the Approach of Dynamical System

The bifurcations of traveling wave solutions of the Broer–Kaup system are investigated and all possible exact parametric representations of the smooth and peaked solitary waves are presented.     

Properties and Preparation of Chitosan/Silanol Quaternary Ammonium Modified Silica Hybrids Using Sol–Gel Process

Chitosan/modified silica nanocomposites, with a sol–gel process being used to prepare a silanol quaternary ammonium modified silica possessing antimicrobial activity, were investigated, as well as the thermal properties, morphology, optical, mechanical, antimicrobial, and adsorption properties of this type of nanocomposite. Grafting of the modifier onto nanosilica was confirmed through the Fourier transform infrared (FTIR) spectra. X-ray diffraction patterns indicated that the chitosan structure was not disrupted from the incorporation of the modified silica. Fracture surfaces with no clear micro-phase separation were observed by scanning electron microscopy (SEM), which indicated the good interaction of chitosan and the modified silica. The organic modifier tended to cause the aggregation of the modified silica at higher content on a submicron scale based on transmission electron microscopy (TEM) analysis, which might be due to a decrease of the stability factor originating from the negative charges on silica. With the introduction of modified silica, the optical transmittance decreased at higher organic modifier content in agreement with TEM analysis. The elongation at break remained largely unchanged, but tensile strength and Young's moduli deteriorated in modified silica filled systems in comparison with pure silica filled systems. The introduction of the organic modified silica gave a higher antibacterial activity. All nanocomposites were capable of chelating Cu (II) as well as Fe (III) at a different degree. Thus, the prepared chitosan/modified silica nanocomposites exhibited both antimicrobial and chelating properties.     

Persistence Properties and Unique Continuation of Solutions to a Two-component Camassa–Holm Equation

We will consider a two-component Camassa–Holm system which arises in shallow water theory. The present work is mainly concerned with persistence properties and unique continuation to this new kind of system, in view of the classical Camassa–Holm equation. Firstly, it is shown that there are three results about these properties of the strong solutions. Then we also investigate the infinite propagation speed in the sense that the corresponding solution does not have compact spatial support for t > 0 though the initial data belongs to C₀^￥(BbbR)C_{0}^{infty}(Bbb{R}).     

Theoretical Approach to Investigation of the Magnetic and Magnetocaloric Properties of Heusler Ni–Mn–Ga Alloys

Physics of the Solid State - The magnetic and magnetocaloric properties of Heusler Ni2&nbsp;+&nbsp;xMn1&nbsp;–&nbsp;xGa alloys (x = 0.16, 0.18, and 0.3) have been studied...     

An Approach to Biochemical Imaging of Heterogeneity in the Bio—tissue Simultaneously Using the Data of Reflectance and Transmittance of Diffuse—Photon Density Waves

An algorithm for the biochemical imaging of heterogeneity in the bio-tissue with finite parallel-plane geometry simultaneously using the data of reflectance and transmittance of diffuse-photon density waves is presented.In this algorithm,the priori knowledge of heterogeneity is not needed,This algorithm is suitable for the imaging of heterogeneity in the large volume tissue and is small organs.To reduce the errors produced by the algorithm,it is suggested that the experiment should be performed in two steps,at first step the light source should be placed at one boundary to measure the data of reflectance and transmittance,and these data are used to construct the heterogeneous function in the half space close to the light source;at the second step the light source should be placed at another boundary to measure the data of reflectance and transmittance,these data are used to construct the heterogeneous function in another half space closed to the light source;after taking above two steps the heterogeneous function in the whole space is constructed.     

Using X-PEEM to study biomaterials: Protein and peptide adsorption to a polystyrene–poly(methyl methacrylate)-b-polyacrylic acid blend

Recent synchrotron-based soft X-ray photoemission electron microscopy (X-PEEM) studies of protein and peptide interaction with phase segregated and patterned polymer surfaces in the context of optimization of candidate biomaterials are reviewed and a study of a new system is reported. X-PEEM and atomic force microscopy (AFM) were used to investigate the morphology of a phase-segregated thin film of a polystyrene/poly(methyl methacrylate)-b-polyacrylic acid (PS/PMMA-PAA) blend, and its interactions with negatively charged human serum albumin (HSA) and positively charged SUB-6 (a cationic antimicrobial peptide, RWWKIWVIRWWR-NH₂) at several pHs. At neutral pH, where the polymer surface is partially negatively charged, HSA and SUB-6 peptide showed contrasting adsorption behavior which is interpreted in terms of differences in their electrostatic interactions with the polymer surface.