Teaching of process analytical chemistry

In the teaching of analytical chemistry for chemical engineering students it is essential today to teach the chemical analysis of dynamic systems, not only in the process control of the modern technological systems, where the control of composition or structure of different material streams is necessary, but also in all other instances where analysis, decision and intervention follow each other, forming a closed cycle. Teaching can be made effective if students already have a knowledge of the basic disciplines (including analytical chemistry). The schedule of the teaching programme should include the mathematical statistical treatment of process signals, quality of the signals, signal-improvement methods, characteristics of instruments, calibration and an introduction to sensors, analysers suitable for continuous or periodical measurements and local area networks. As practical exercizes an apparatus for investigation of the dynamic properties of a thermoanalytical detector system, a computer program for simulating process variables and the control loop including the measuring system are presented.     

The Process Analytical Technology initiative and multivariate process analysis, monitoring and control

Process analytical technology is an essential step forward in pharmaceutical industry. Real-time analyzers will provide timely data on quality properties. This information combined with process data (temperatures, flow rates, pressure readings) collected in real time can become a powerful tool for this industry, for process understanding, process and quality monitoring, abnormal situation detection and for improving product quality and process reliability. A very important tool for this achievement is the multivariate analysis. Dr. Theodora Kourti is Research Manager in the McMaster Advanced Control Consortium (MACC) and Adjunct Professor in the Chemical Engineering Department at McMaster University. She is the co-recipient of the 2003 University – Industry Synergy Award for Innovation, given by the Natural Science & Engineering Research Council of Canada. Dr. Kourti has been working on Multivariate Statistical Methods for Process and Product Improvement and Abnormal Situation Detection in Process Industries since 1992 and has been involved in more than 80 major industrial applications in North America and Europe. These are either off-line or real-time applications for batch and continuous processes, in diverse industries such as Chemicals, Pharmaceuticals, Semiconductor, Mining, Pulp and Paper, Petrochemicals, Photographic and Steel Industry. She has published extensively in this area and has provided training for numerous industrial practitioners.     

Application of wet chemistry techniques to process analysis and control

The availability of reliable and rugged automatic titrators, flow-injection analysers and ion chromatographs provides opportunities for their application in industrial process analysis. The control of industrial processes such as the removal of sulphur during gas treatment presents a challenge as accurate on-line and in-line analysers are required. The application of automatic titrators and ion chromatographs to the compositional analysis of caustic and alkanolamine gas sweetening solutions is described. Comparisons with other techniques such as flow-injection analysis and ultraviolet and near-infrared spectrometry are made and the pertinent features and benefits of each are discussed.     

Four-channel enzyme thermistor system for process monitoring and control in biotechnology

A newly developed four-channel enzyme thermistor system is presented and its application to biotechnological process monitoring is discussed. Different sugars were detected on-line during the cultivation of Cephalosporium acremonium and Bacillus licheniformis on technical media and during a starch hydrolysis process with immobilized thermostable enzymes. Immobilized enzymes and entrapped microorganisms were used as biological compounds in this biosensor.     

Sequential injection: a new concept for chemical sensors,process analysis and laboratory assays

Established flow-injection techniques allow advanced solution handling for laboratory purposes, but chemical sensing and continuous monitoring of chemical processes require dramatically simplified flow schemes and instrumentation with the potential for miniaturization and an inherent ruggedness. Considerations based on the random walk model have led to the concept of sensor injection and sequential injection analysis. This new approach to automated analysis is designed to fill a gap in present flow-injection methodology.     

Photoacoustic spectroscopy for process analysis

Photoacoustic spectroscopy (PAS) is based on the absorption of electromagnetic radiation by analyte molecules. The absorbed energy is measured by detecting pressure fluctuations in the form of sound waves or shock pulses. In contrast to conventional absorption spectroscopy (such as UV/Vis spectroscopy), PAS allows the determination of absorption coefficients over several orders of magnitude, even in opaque and strongly scattering samples. Small absorption coefficients, such as those encountered during trace gas monitoring, can be detected with cells with relatively short pathlengths. Furthermore, PA techniques allow absorption spectra of solid samples (including powders, chips or large objects) to be determined, and they permit depth profiling of layered systems. These features mean that PAS can be used for on-line monitoring in technical processes without the need for sample preparation and to perform depth-resolved characterization of industrial products. This article gives an overview on PA excitation and detection schemes employed in analytical chemistry, and reviews applications of PAS in process analytical technology and characterization of industrial products.     

The role of analytical chemistry in process quality control

The growing need for quality supervision and control in production processes is briefly outlined. After a summary of available process analytical devices, and a short discussion of their possibilities and limitations, an alternative approach is discussed. This approach is based on the development of a dynamic process model which allows on-line quality predictions to be made by means of so- called state estimators. The advantage is that it becomes possible to use quantities which give only indirect information about the product quality, but which are more readily accessible for continuous or on-line monitoring in earlier stages of the process.     

Process analysis

Process analysis, the means whereby chemical composition may be assessed or inferred for industrial processes, is part of measurement science which, in combination with sound theory, engineering, construction, operation and maintenance, is vital to safety, efficiency and the environment. A modern general measurement development strategy based on mimicking successful biological evolution is discussed. The measurement system requirements for sampling, transduction and signal processing are examined before advances made since ANATECH 86 are indicated. A framework is also given of “rules for success” based on a study of human or business needs, checking assumptions, thinking widely, transference of skills and entrepreneurism.     

Applications of the deferred standard technique in process gas chromatography

Three applications of the deferred standard (DS) technique in on-line gas chromatographic analysis with a rotary injection valve are reported. It is demonstrated how both absolute and relative measurements are affected by several deviations of the experimental conditions, such as atmospheric pressure, sample injection during either flow or stopped-flow conditions and instrumental settings (carrier gas flow-rate, column oven temperature, detector bridge current) of the analytical system. It is shown that the relative DS concept provides an excellent means of improving the reliability of the analytical equipment. Under standard conditions, accurate results were obtained with a relative standard deviation < 1%. Significant deviations in the instrumental settings affected the accuracy of the final analytical results by less than 4%. It is further shown how the DS technique can be applied to obtain early information on maintenance requirements of the system. A diagnostic table is included that relates observed changes with time of the signals, obtained with a thermal conductivity detector, to possible maintenance requirements.     

The current state of analytical control in Lithuania

In Lithuania research and development in chemical analysis are concentrated in scientific institutes and universities. The main fields of interest focus on biosensors, electrochemical sensors, sampling techniques and methods, study of atomization processes in spectrochemical analysis and noise evaluation in analytical measurements. Some laboratories also take part in international environmental monitoring programmes. There are about 50 researchers at the Ph.D. level engaged in analytical chemistry and several hundred technicians specialized in the field of analytical control. About one hundred chemical laboratories are active in scientific institutes, universities and factories. Specialized laboratories of chemical analysis are at the disposal of Environmental Control and Health Protection Departments and forensic investigation organizations. So far no laboratories are accredited according to the ISO 9000 norms. Special courses on analytical chemistry are offered at a few schools of higher education in the country. Only at the Department of Analytical Chemistry of the University of Vilnius specialized programmes are available to postgraduate students working towards a Ph.D. to improve their skills in current techniques of analytical chemistry. Recently the Technical Committee TC-16 for Chemical Analysis was formed within the standardization system of Lithuania. Its main activities are centered on issues such as national terminology, certified reference materials (CRMs), analytical methods and analytical quality assurance. There are numerous problems related to national terminology, the preparation of special documents in the field of analytical control and the production of regional environmental CRMs. Problems, also arise in obtaining and using CRMs for analytical instrument calibration and validation.     

A device for fully automated on-site process monitoring and control of trihalomethane concentrations in drinking water

An instrument designed for fully automated on-line monitoring of trihalomethane concentrations in chlorinated drinking water is presented. The patented capillary membrane sampling device automatically samples directly from a water tap followed by injection of the sample into a gas chromatograph equipped with a nickel-63 electron capture detector. Detailed studies using individual trihalomethane species exhibited method detection limits ranging from 0.01–0.04 μg L⁻¹. Mean percent recoveries ranged from 77.1 to 86.5% with percent relative standard deviation values ranging from 1.2 to 4.6%. Out of more than 5200 samples analyzed, 95% of the concentration ranges were detectable, 86.5% were quantifiable. The failure rate was less than 2%. Using the data from the instrument, two different treatment processes were optimized so that total trihalomethane concentrations were maintained at acceptable levels while reducing treatment costs significantly. This ongoing trihalomethane monitoring program has been operating for more than ten months and has produced the longest continuous and most finely time-resolved data on trihalomethane concentrations reported in the literature.     

Constant Cwall ultrafiltration process control

Ultrafiltration processes normally operate with constant transmembrane pressure. The tradition of such control derives from its inherent simplicity. Both fundamental and practical considerations suggest, however, that ultrafiltration processes should be controlled by maintaining a constant wall concentration (C_w) of fully retained solutes. Since protein sieving, solubility, and adsorption losses as well as time and area optimization are dependent on C_w, we investigated a control strategy using constant C_w instead of constant transmembrane pressure. We explored three different strategies for such control and evaluated the theoretical and industrial implications for single solute systems. The effects of solute wall concentration on process time and product yield were also evaluated. Implementation of this technology required the development of a novel methodology for determination of mass transfer coefficients. The use of C_w technology also led to the development of new optimization schemes for both concentration and diafiltration. Industrial scale processes using constant C_w control have been successfully implemented on several recombinant DNA derived human protein pharmaceuticals. Constant C_w control has eliminated variability in process time, enhanced product yields, and provided insurance of tight protein product quality specifications. Optimum process design based on fundamental filtration theory has replaced empirical development procedures.     

The analysis of process gases: a review

 A general review of key issues involved in the analysis of process gases is presented. The reasons for such measurements – which include safety, quality, environmental and economic factors are considered. The technical issues arising from these measurements are dependent upon a variety of factors, including the overall sampling system, the type of analytical instrumentation, methods of data collection and the specified calibration protocols. The use of gas calibration cylinders as transfer standards is detailed and issues of stability and traceability to reference material discussed. Received: 1 March 2000 / Accepted: 31 March 2000     

On-line fermentation gas analysis: Error analysis and application of mass spectrometry

On-line fermentation gas analysis is of general interest because it permits the determination of metabolic rates in almost any biological process using living organisms. The consumption and production of gases (O₂, CO₂, CH₄, etc.) and volatile compounds may be determined without causing any risk of infection. Elemental balancing permits the determination of other metabolic rates if the stoichiometry is known. This was studied with the production of poly-β-hydroxybutyrate (PHB) by Alcaligenes latus. Estimations were based on the measurement of gas partial pressure and flow-rates, pH and alkali consumption rate. Experiments with a small quadrupole mass spectrometer showed unacceptable error propagation. Therefore, dynamic error propagation for all rates was studied using simulation. It was found that, for example, a 1% relative offset-calibration error for oxygen can result in an error in PHB estimation of > 50%. It is suggested that this culture is used in combination with elemental balancing for thorough tests of the accuracy of on-line gas analysis equipment. An on-line process gas analyser based on a quadrupole mass spectrometer (Balzers PGM 407) gave the following precision values (abs. vol.?%) during cultivation of Bacillus subtilis: nitrogen (m/z 14), 0.024; oxygen (m/z 32), 0.020; argon (m/z 40), 0.0011; and carbon dioxide (m/z 44), 0.0034. These values, combined with automatic recalibration, would be sufficient for reasonable estimation of PHB, biomass and substrates.     

On-line analysis of polymer melt processes

Molten polymer process streams are difficult to analyze either in- or on-line because of sampling problems due to the high temperature and viscosity of the molten state. Real-time monitoring of chemical compositions in these processes can significantly improve safety and product quality and minimize process costs and waste. The information content of the mid-infrared spectrum combined with the recent development of rugged process Fourier transform (FT) IR spectrometers is stimulating the application of process FT-IR to industrial polymer melt processes. Sampling considerations for polymer melts are reviewed. Also, the use of FT-IR spectrometry for on-line measurements of the polymer composition for polymer blends and copolymers in the melt, and the question of how this information could be used to monitor and control the quality of the product given by the process are discussed.     

On-line process analysis and control in biotechnology

Measuring techniques can be developed and adapted for the characterization of bioreactors, for on-line process analysis and for the determination of biological parameters of cells during fermentation. Mathematical models can be formulated for bioreactors and cell regulation and a combined model for these can be reduced for use in process control. Microprocessors and minicomputers give further scope for data acquisition, model implementation and process control.     

Effluent analysis in analytical chemistry: an overview

This review summarizes and discusses effluent analysis, focusing on the methods and techniques that have been most frequently described in the literature since 1975. The methods are classified into four main categories: (1) physical and chemical properties; (2) inorganic metals analysis; (3) inorganic non-metallic analysis; (4) organic analysis.     

Flow injection analysis in on-line process control

Flow injection systems are serious candidates for a new generation of chemical on-line analyzers because there is a growing interest in instruments that combine versatility with the possibility of attaining high sampling frequencies. For real on-line applications the instrument and its component parts have to meet the highest standards with respect to reliability and maintenance. These aspects are considered in some detail, and some industrial applications are briefly discussed.     

Perspectives in process analysis

Process analysis is a transdisciplinary technology. Process chemists, process engineers, chemometricians, and many other technologists must work together and put more emphasis on the essentials of science of each discipline. This perspective analyzes potential strategies for intelligent production in the future. It emphasizes the need for a holistic approach where multimodality will be a bedrock supporting the production of smart materials in smart factories. Copyright © 2013 John Wiley & Sons, Ltd.