On-line estimation of key process variables based on kernel partial least squares in an industrial cokes wastewater treatment plant

A kernel-based algorithm is potentially very efficient for predicting key quality variables of nonlinear chemical and biological processes by mapping an original input space into a high-dimensional feature space. Nonlinear data structure in the original space is most likely to be linear at the high-dimensional feature space. In this work, kernel partial least squares (PLS) was applied to predict inferentially key process variables in an industrial cokes wastewater treatment plant. The primary motive was to give operators and process engineers a reliable and accurate estimation of key process variables such as chemical oxygen demand, total nitrogen, and cyanides concentrations in real time. This would allow them to arrive at the optimum operational strategy in an early stage and minimize damage to the operating units as shock loadings of toxic compounds in the influent often cause process instability. The proposed kernel-based algorithm could effectively capture the nonlinear relationship in the process variables and show far better performance in prediction of the quality variables compared to the conventional linear PLS and other nonlinear PLS method.     

Process analysis,monitoring and diagnosis,using multivariate projection methods

Multivariate statistical methods for the analysis, monitoring and diagnosis of process operating performance are becoming more important because of the availability of on-line process computers which routinely collect measurements on large numbers of process variables. Traditional univariate control charts have been extended to multivariate quality control situations using the Hotelling T² statistic. Recent approaches to multivariate statistical process control which utilize not only product quality data (Y), but also all of the available process variable data (X) are based on multivariate statistical projection methods (principal component analysis, (PCA), partial least squares, (PLS), multi-block PLS and multi-way PCA). An overview of these methods and their use in the statistical process control of multivariate continuous and batch processes is presented. Applications are provided on the analysis of historical data from the catalytic cracking section of a large petroleum refinery, on the monitoring and diagnosis of a continuous polymerization process and on the monitoring of an industrial batch process.     

Quantitative structure–activity relationships study of herbicides using neural networks and different statistical methods

A series of herbicidal materials, N-phenylacetamides (NPAs), has been studied for their Quantitative Structure–Activity Relationships (QSAR). The molecular structure as well as the activity data were taken from literature [O. Kirino, C. Takayama, A. Mine, Quantitative structure relationships of herbicidal N-(1-methyl-1-phenylethyi) phenylacetamides, Journal Pesticide Science 11 (1986) 611–617]. The independent variables used to describe the structure of compounds consisted of seven physicochemical properties, including the mode of molecular connection, steric factor, hydrophobic parameter, etc. Fifty different compounds constitute a sample set which is divided into two groups, 47 of them form a training set and the remaining three a checking set. Through a systematic study by using the classic multivariate analysis such as the Multiple Linear Regression (MLR), the Principal Component Analysis (PCA), and the Partial Least Squares (PLS) Regression, several QSAR models were established. For finding a better way to depict the nonlinear nature of the problem, multi-layered feed-forward (MLF) neural networks (NNs) was employed. The results indicated that the conventional multivariate analysis gave larger prediction errors, while the NNs method showed better accuracy in both self-checking and prediction-checking. The error variance of predictions made by NNs was the smallest among the all methods tested, only around half of the others.     

A novel approach for development of a multivariate calibration model using a Doehlert experimental design: Application for prediction of key gasoline properties by Near-infrared Spectroscopy

Alternative methods for quality control in the petroleum industry have been obtained using Near-infrared Spectroscopy (NIRS) combined with multivariate techniques such as PLS (Partial Least-Square). The process of development and refinement of PLS models usually follows a nonsystematic and univariate procedure. The Standard Error of Cross Validation (SECV), the Standard Error of Prediction (SEP) and the determination coefficient (r²_regr.) are usually the only guides used in pursuit of the best model. In the present work, a novel approach was proposed using a Doehlert experimental design with three input variables (wavenumber range, preprocessing technique and regression/validation technique) varied at 5, 7 and 3 levels, respectively. Besides SECV, SEP and r²_regr., some additional response variables, such as the slope, r² and p_value from the external validation, as well as the number of PLS factors, were simultaneously assessed to find the optimum conditions for PLS modeling. The optimum setting for each input variable was simultaneously defined through a multivariate approach using a desirability function. With the proposed approach, the main and interaction effects could also be investigated. The methodology was successfully applied to obtain PLS models to monitor the gasoline quality through the process of product loading in trucks. To prevent product contamination or adulteration, fast prediction of key properties was obtained from FT-NIR spectra within the 7300-3900 cm^− 1 region with SECV in the range 0.04-0.63% w/w for composition (Aromatics, Saturates, Olefins and Benzene) and 0.0008 for Relative Density 20/4 °C. Each optimized PLS model was obtained with less than 40 modeling runs, demonstrating the efficiency of the proposed approach.     

Analysis for a two-dissimilar-component cold standby repairable system with repair priority

In this paper, a cold standby repairable system consisting of two dissimilar components and one repairman is studied. Assume that working time distributions and repair time distributions of the two components are both exponential, and Component 1 has repair priority when both components are broken down. After repair, Component 1 follows a geometric process repair while Component 2 obeys a perfect repair. Under these assumptions, using the perfect repair model, the geometric process repair model and the supplementary variable technique, we not only study some important reliability indices, but also consider a replacement policy T, under which the system is replaced when the working age of Component 1 reaches T. Our problem is to determine an optimal policy T^? such that the long-run average loss per unit time (i.e. average loss rate) of the system is minimized. The explicit expression for the average loss rate of the system is derived, and the corresponding optimal replacement policy T^? can be found numerically. Finally, a numerical example for replacement policy T is given to illustrate some theoretical results and the model's applicability.     

Proteomic profile analysis and biomarker discovery from mass spectra using independent component analysis combined with uncorrelated linear discriminant analysis

A strategy based on Independent Component Analysis (ICA) and Uncorrelated linear discriminant analysis (ULDA) was proposed for proteomic profile analysis and potential biomarker discovery from proteomic mass spectra of cancer and control samples. The method mainly includes 3 steps: (1) ICA decomposition for the mass spectra; (2) selection of discriminatory independent components (ICs) using nonparametric Mann-Whitney U-test; and (3) selection of special peaks (m/z locations) as potential biomarkers by executing of ULDA on a mass spectra data set which was reconstructed with the m/z locations that collected from the selected discriminatory ICs. A colorectal cancer data set and an ovarian cancer data set were analyzed with the proposed method. As results, 9 and 10 m/z locations were selected as potential biomarkers for the colorectal and ovarian cancer data set respectively. The classification results of ULDA using the selected potential biomarkers yielded better results than fisher discriminant analysis (FDA) and principal component analysis (PCA), and could distinguish the disease samples from healthy controls on the independent test sets with 100% of sensitivities and specificities for the colorectal cancer dataset and 100% of sensitivity and 96.77% of specificity for the ovarian cancer dataset.     

State-space independent component analysis for nonlinear dynamic process monitoring

The cost effective benefits of process monitoring will never be over emphasised. Amongst monitoring techniques, the Independent Component Analysis (ICA) is an efficient tool to reveal hidden factors from process measurements, which follow non-Gaussian distributions. Conventionally, most ICA algorithms adopt the Principal Component Analysis (PCA) as a pre-processing tool for dimension reduction and de-correlation before extracting the independent components (ICs). However, due to the static nature of the PCA, such algorithms are not suitable for dynamic process monitoring. The dynamic extension of the ICA (DICA), similar to the dynamic PCA, is able to deal with dynamic processes, however unsatisfactorily. On the other hand, the Canonical Variate Analysis(CVA) is an ideal tool for dynamic process monitoring, however is not sufficient for nonlinear systems where most measurements follow non-Gaussian distributions. To improve the performance of nonlinear dynamic process monitoring, a state space based ICA (SSICA) approach is proposed in this work. Unlike the conventional ICA, the proposed algorithm employs the CVA as a dimension reduction tool to construct a state space, from where statistically independent components are extracted for process monitoring. The proposed SSICA is applied to the Tennessee Eastman Process Plant as a case study. It shows that the new SSICA provides better monitoring performance and detect some faults earlier than other approaches, such as the DICA and the CVA.     

Kalman filter for updating the coefficients of regression models. A case study from an activated sludge waste-water treatment plant

A Kalman filter was developed to overcome the problems caused by process drifting. Different types of models were used to predict response variables of an activated sludge waste-water treatment plant. These models were constructed using MLR, PCR, and PLS. The MLR-type regression coefficients were calculated for both the PCR and PLS models. After that, the Kalman filter was used to estimate these coefficients, recursively. Both the PCR and PLS `inner relation' coefficient vectors were also estimated in this way and the results were then compared. The effect of the number of variables was also briefly studied. The testing was carried out using sequential process data. The prediction ability was measured by a Q²-value as a function of a lag in the updating of the coefficients.     

Uncover the path from PCR to PLS via elastic component regression

This contribution introduces Elastic Component Regression (ECR) as an explorative data analysis method that utilizes a tuning parameter α ∈ [0,1] to supervise the X-matrix decomposition. It is demonstrated theoretically that the elastic component resulting from ECR coincides with principal components of PCA when α = 0 and also coincides with PLS components when α = 1. In this context, PCR and PLS occupy the two ends of ECR and α ∈ (0,1) will lead to an infinite number of transitional models which collectively uncover the model path from PCR to PLS. Therefore, the framework of ECR shows a natural progression from PCR to PLS and may help add some insight into their relationships in theory. The performance of ECR is investigated on a series of simulated datasets together with a real world near infrared dataset. (The source codes implementing ECR in MATLAB are freely available at http://code.google.com/p/ecr/.)     

Linear and nonlinear modeling for simultaneous prediction of dissolved oxygen and biochemical oxygen demand of the surface water — A case study

The paper describes linear and nonlinear modeling for simultaneous prediction of the dissolved oxygen (DO) and biochemical oxygen demand (BOD) levels in the river water using the set of independent measured variables. Partial least squares (PLS2) regression and feed forward back propagation artificial neural networks (FFBP ANNs) modeling methods were applied to predict the DO and BOD levels using eleven input variables measured monthly in the river water at eight different sites over a period of ten years. The performance of the models was assessed through the root mean squared error (RMSE), the bias, the standard error of prediction (SEP), the coefficient of determination (R²), the Nash-Sutcliffe coefficient of efficiency (E_f), and the accuracy factor (A_f), computed from the measured and model-predicted values of the dependent variables (DO, BOD). Goodness of the model fit to the data was also evaluated through the relationship between the residuals and the model predicted values of DO and BOD, respectively. Although, the model predicted values of DO and BOD by both the linear (PLS2) and nonlinear (ANN) models were in good agreement with their respective measured values in the river water, the nonlinear model (ANN) performed relatively better than the linear one. Relative importance and contribution of the input variables to the identified ANN model was evaluated through the partitioning approach. The developed models can be used as tool for the water quality prediction.     

Sparse partial least-squares regression and its applications to high-throughput data analysis

The partial least-squares (PLS) method is designed for prediction problems where the number of predictors is larger than the number of training samples. PLS is based on latent components that are linear combinations of all of the original predictors, so it automatically employs all predictors regardless of their relevance. This will potentially compromise its performance, but it will also make it difficult to interpret the result. In this paper, we propose a new formulation of the sparse PLS (SPLS) procedure to allow both sparse variable selection and dimension reduction. We use the standard L₁-penalty and the unbounded penalty of [1]. We develop a computing algorithm for SPLS by modifying the nonlinear iterative partial least-squares (NIPALS) algorithm, and illustrate the method with an analysis of a cancer dataset. Through the numerical studies we find that our SPLS method generally performs better than the standard PLS and other existing methods in variable selection and prediction.     

基于近红外光谱分析技术的液态水性油墨印刷品 颜色预测模型

针对印刷品颜色离线检测存在滞后、检测不精准等问题,提出基于近红外光谱分析技术的液态水性油墨印刷品颜色预测模型。用多元散射校正（MSC） 、标准正态变换（SNV）和卷积平滑滤波器（SG）对原始光谱数据进行预处理,将原始光谱数据及预处理后的光谱数据分别与印刷品的Lab值建立偏最小二乘回归（PLSR）和主成分回归（PCR）两种预测模型。结果表明,基于MSC预处理的PLSR预测模型的预测精度最高,L、a、b值的R2分别高达0.9885, 0.9879和0.9938,预测颜色的平均色差约为0.71。液态水性油墨的近红外光谱可以精确预测印刷品颜色,为印刷品的在线检测提供了新思路。     

Coupling subband decomposition and independent component regression for quantitative NIR spectroscopy

In this paper, a new method is proposed for coupling digital bandpass filtering with independent component regression (ICR) to improve the quality of the raw absorbance spectra in quantitative NIR spectroscopy. The proposed model, referred to as SDICR, is based on a subband decomposition independent component analysis (SDICA) model coupled with ICR regression. The SDICA is used to select the optimal parameters of the digital bandpass filter and to determine the most independent subcomponents of the original sources, so the standard ICA methods can be used. The efficiency of the proposed model is validated using mixtures composed of glucose, urea and triacetin in a phosphate buffer solution in a non-controlled environment. The proposed model decreases the standard error of prediction (SEP) from 29.1 mg/dL for ICR to only 18.6547 mg/dL using 10 subbands.     

Estimation of lean meat content in pig carcasses using X-ray Computed Tomography and PLS regression

Lean meat percentage (LMP) is an important carcass quality parameter. The aim of this work is to obtain a calibration equation for the Computed Tomography (CT) scans with the Partial Least Square Regression (PLS) technique in order to predict the LMP of the carcass and the different cuts and to study and compare two different methodologies of the selection of the variables (Variable Importance for Projection — VIP- and Stepwise) to be included in the prediction equation. The error of prediction with cross-validation (RMSEPCV) of the LMP obtained with PLS and selection based on VIP value was 0.82% and for stepwise selection it was 0.83%. The prediction of the LMP scanning only the ham had a RMSEPCV of 0.97% and if the ham and the loin were scanned the RMSEPCV was 0.90%. Results indicate that for CT data both VIP and stepwise selection are good methods. Moreover the scanning of only the ham allowed us to obtain a good prediction of the LMP of the whole carcass.     

An adaptive step-down procedure for fault variable identification

In a process with a large number of process variables (high-dimensional process), identifying which variables cause an out-of-control signal is a challenging issue for quality engineers. In this paper, we propose an adaptive step-down procedure using conditional T² statistic for fault variable identification. While existing procedures focus on selecting variables that have strong evidence of a change, the proposed step-down procedure selects a variable having the weakest evidence of a change at each step based on the variables that are selected in previous steps. The information of selected unchanged variables is effectively utilised in obtaining a powerful conditional T² test statistic for identifying the changed elements of the mean vector. The proposed procedure is designed to utilise the correlation information between fault and non-fault variables for the efficient fault variables identification. Further, the simulation results show that the proposed procedure has the better diagnostic performance compared with existing methods in terms of fault variable identification and computational complexity, especially when the number of the variables is high and the number of fault variables is small.     

On-line predictions of the aspen fibre and birch bark content in unbleached hardwood pulp, using NIR spectroscopy and multivariate data analysis

An on-line fibre-based near-infrared (NIR) spectrometric analyser was adapted for on-site process analysis at an integrated paperboard mill. The analyser uses multivariate techniques for the quantitative predication of the aspen fibre (aspen) and the birch bark contents of sheets of unbleached hardwood pulp. The NIR analyser is a prototype constructed from standard NIR components. The spectroscopic data was processed by using principal component analysis (PCA) and partial least square (PLS) regression. Three sample sets were collected from three experimental designs, each composed of known pulp contents of birch, aspen and birch bark. Sets 1 and 2 were used for model calibration and set 3 was used to validate the models. The PLS model that produced the best predictions gave an error of prediction (RMSEP) of 13% for aspen and less than 2% for birch bark. Eight components resulted in an R²X of 99.3%, R²Y of 99.6%, and Q² of 95.3%. For additional validation of aspen, three unbleached hardwood samples from the mill's production were calculated to lie between − 7% and + 6%, regarding to the PLS model. When vessel cells were counted under a light microscope a value for the aspen content of 4.7% was obtained. The predictive models evaluated were suitable for quality assessments rather than quantitative determination.     

Determination of glucose concentration from NIR spectra using independent component regression

In this paper, a new model based on independent component regression (ICR) is proposed to predict the glucose concentration from near infrared (NIR) spectra. The efficiency of the proposed model is validated using mixtures composed of glucose, urea and triacetin. The whole experiments were carried out in a non-controlled environment or sample conditions to show that the proposed model can suppress effectively most of the experimental variations. The proposed model decreases the standard error of prediction (SEP) from 35.59 mg/dL for Partial Least Square regression (PLS) and from 29.1 mg/dL for ICR to only 24.1 mg/dL.     

A boosting approach for understanding out-of-control signals in multivariate control charts

The most widely used tools in statistical quality control are control charts. However, the main problem of multivariate control charts, including Hotelling's T ² control chart, lies in that they indicate that a change in the process has happened, but do not show which variable or variables are the source of this shift. Although a number of methods have been proposed in the literature for tackling this problem, the most usual approach consists of decomposing the T ² statistic. In this paper, we propose an alternative method interpreting this task as a classification problem and solving it through the application of boosting with classification trees. The classifier is then used to determine which variable or variables caused the change in the process. The results prove this method to be a powerful tool for interpreting multivariate control charts.