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Modular chemical process intensification can dramatically improve energy and process efficiencies of chemical processes through enhanced mass and heat transfer, application of external force fields, enhanced driving forces, and combinations of different unit operations, such as reaction and separation, in single-process equipment. These dramatic improvements lead to several benefits such as compactness or small footprint, energy and cost savings, enhanced safety, less waste production, and higher product quality. Because of these benefits, process intensification can play a major role in industrial and manufacturing sectors, including chemical, pulp and paper, energy, critical materials, and water treatment, among others. This article provides an overview of process intensification, including definitions, principles, tools, and possible applications, with the objective to contribute to the future development and potential applications of modular chemical process intensification in industrial and manufacturing sectors. Drivers and barriers contributing to the advancement of process intensification technologies are discussed.

Chitin is high in crystallinity in its natural form and does not dissolve into high temperature water (HTW), which often leads to decomposition reactions such as hydrolysis, deacetylation and dehydration when hydrothermally processed. In this work, we investigated the reactions of mechanically milled chitin in HTW. Mechanical milling pretreatment combined with HTW treatment improved the liquefaction of chitin giving a maximum water soluble fraction of 80%, where the untreated chitin was 55%. The reaction mechanism of the milled and raw chitin in HTW was shown to be different. For milled chitin, the dissolution of chitin occurred during the heating period to supercritical water conditions (400°C) at short reaction times (1 min). Extended reaction time (10 min) led to decomposition products and aromatic char formation. For raw chitin, the dissolution of chitin in HTW did not occur, due to its high crystallinity, so that liquefaction proceeded via decomposition reactions., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The interlaminar shear response is studied for carbon nanofiber (CNF) modified out-of-autoclave-vacuum-bag-only (OOA-VBO) carbon fiber reinforced plastic (CFRP). Commercial OOA-VBO prepregs were coated with a CNF modified epoxy solution and a control epoxy solution without CNF to make CNF modified samples and control samples, respectively. Tensile testing was used to study the in-plane shear performance of [± 45°]4s composite laminates. Significant difference in failure modes between the control and CNF modified CFRPs was identified. The control samples experienced half-plane interlaminar delamination, whereas the CNF modified samples experienced a localized failure in the intralaminar region. Digital image correlation (DIC) surface strain results of the control sample showed no further surface strain increase along the delaminated section when the sample was further elongated prior to sample failure. On the other hand, the DIC results of the CNF modified sample showed that the surface strain increased relatively and uniformly across the CFRP as the sample was further elongated until sample failure. The failure mode evidence along with microscope pictures indicated that the CNF modification acted as a beneficial reinforcement inhibiting interlaminar delamination.

Mass spectrometry (MS) has been intensively used in the field of flavor and fragrance since its beginning in the 1950s, and it remains an essential technique for current and future research in this field. After a short historical section on the introduction and development of MS at Firmenich, this work reviews the main applications of MS-based techniques published by Firmenich researchers over the past 5 years. It exemplifies the use of gas chromatography (GC)-MS for the discovery of new odorant - hence volatile - molecules in a broad range of natural products, such as fruits, meats, and vegetables. Non-volatile compounds play a major role in taste attributes and are also possible precursors of odorant molecules. Their identification by liquid chromatography (LC)-MS in the context of malodor generation from sweat is a typical example of such a relationship. With their high selectivity and sensitivity, GC-MS and LC-MS instruments are used in the fields of flavor and fragrance not only for identification, but also as unique tools for the accurate quantitation of compounds in complex matrices. This is particularly important for regulatory analyses such as dosage of potential allergens in perfumes and for the development of delivery systems. Finally, because of the rapid response time of MS, the kinetics of processes such as the release of flavors in the mouth during food consumption can be monitored by direct sampling into the mass spectrometer.

The nitric acid plant of a domestic petrochemical complex is designed to annually produce 56,400 metric tons (based on 100% nitric acid). In the present work, radial-flow spherical bed reactor (RFSBR) for selective catalytic reduction of nitric oxides (NO(x)) from the stack of this plant was modelled and compared with the conventional radial-flow reactor (CRFR). Moreover, the proficiency of a radial-flow (water or nitrogen) membrane reactor was also compared with the CRFR which was found to be inefficient at identical process conditions. In the RFSBR, the space between the two concentric spheres is filled by a catalyst. A mathematical model, including conservation of mass has been developed to investigate the performance of the configurations. The model was checked against the CRFR in a nitric acid plant located at the domestic petrochemical complex. A good agreement was observed between the modelling results and the plant data. The effects of some important parameters such as pressure and temperature on NO(x) conversion were analysed. Results show 14% decrease in NO(x) emission annually in RFSBR compared with the CRFR, which is beneficial for the prevention of NO(x) emission, global warming and acid rain.

Setpoint filters are widely used along with a PID controller. The aim of the present paper is to reduce the peak overshoot to a desired/tolerable limit. To design a setpoint filter, numerous methods are available, which need extensive calculations. Moreover, the existing methods need information regarding the process parameters, values of controller settings and are laborious. But the proposed method is very simple and requires only the information about the peak overshoot and peak time of the system response regardless of type and order of the system with arbitrary PID parameters. Several examples are taken to show efficacy of the process., (Copyright © 2011 ISA. Published by Elsevier Ltd. All rights reserved.)

An improved cascade control structure with a modified Smith predictor is proposed for controlling open-loop unstable time delay processes. The proposed structure has three controllers of which one is meant for servo response and the other two are for regulatory responses. An analytical design method is derived for the two disturbance rejection controllers by proposing the desired closed-loop complementary sensitivity functions. These two closed-loop controllers are considered in the form of proportional-integral-derivative (PID) controller cascaded with a second order lead/lag filter. The direct synthesis method is used to design the setpoint tracking controller. By virtue of the enhanced structure, the proposed control scheme decouples the servo response from the regulatory response in case of nominal systems i.e., the setpoint tracking controller and the disturbance rejection controller can be tuned independently. Internal stability of the proposed cascade structure is analyzed. Kharitonov's theorem is used for the robustness analysis. The disturbance rejection capability of the proposed scheme is superior as compared to existing methods. Examples are also included to illustrate the simplicity and usefulness of the proposed method., (Copyright © 2011 ISA. Published by Elsevier Ltd. All rights reserved.)

Workers engaged into the studied production are exposed to occupational factors complex as vapor, gas and aerosol mixture. Metallic mercury vapors and its compounds exceed MAC over 10 times in this mixture, noise level at the enterprise is 10 dB over the maximal allowable level, general vibration is 8 dB over the MAL, the occupational hazards also include unfavorable microclimate, work hardiness and intensity. Psychoemotional state of the workers demonstrate significantly disordered emotions and will, premorbid personality changes, lower memory and attention level, indisposition and mood changes, increased reactive and personal anxiety, decreased performance level. Informative parameter in occupational examination of workers is memory and attention level evaluation.

The temperature control of a polymerization reactor described by Chylla and Haase, a control engineering benchmark problem, is used to illustrate the potential of adaptive control design by employing a self-tuning regulator concept. In the benchmark scenario, the operation of the reactor must be guaranteed under various disturbing influences, e.g., changing ambient temperatures or impurity of the monomer. The conventional cascade control provides a robust operation, but often lacks in control performance concerning the required strict temperature tolerances. The self-tuning control concept presented in this contribution solves the problem. This design calculates a trajectory for the cooling jacket temperature in order to follow a predefined trajectory of the reactor temperature. The reaction heat and the heat transfer coefficient in the energy balance are estimated online by using an unscented Kalman filter (UKF). Two simple physically motivated relations are employed, which allow the non-delayed estimation of both quantities. Simulation results under model uncertainties show the effectiveness of the self-tuning control concept., (Copyright © 2011 ISA. Published by Elsevier Ltd. All rights reserved.)

A new fuel additive, namely solketal tert-butyl ether (STBE), was developed and optimized under continuous flow conditions using a Corning® Advanced-Flow™ glass reactor. STBE was obtained in two steps from glycerol, a renewable building-block produced in large amount in the processing of biodiesel. The advantages of the highly engineered Corning glass reactor included high mixing and heat-exchange efficiency, chemical resistance under corrosive flow conditions and a small hold-up. A robust, continuous, green and safe industrial-scale process is described., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Process intensification follows four main goals: to maximize the effectiveness of intra- and intermolecular events, to give each molecule the same processing experience, to optimize the driving forces/maximize specific interfacial areas, and to maximize the synergistic effects of partial processes. This paper shows how these goals can be reached in reaction and separation systems at all relevant time and length scales and is focused on the structuring of reactors and separation units, on the use of different energy forms to improve the reaction and separation, on combining and superimposing of different phenomena in one integrated unit or reactor, and on the application of oscillations for intensification of reaction and separation processes.

The terminology Novel Process Window unites different methods to improve existing processes by applying unconventional and harsh process conditions like: process routes at much elevated pressure, much elevated temperature, or processing in a thermal runaway regime to achieve a significant impact on process performance. This paper is a review of parts of IMM's works in particular the applicability of above mentioned Novel Process Windows on selected chemical reactions. First, general characteristics of microreactors are discussed like excellent mass and heat transfer and improved mixing quality. Different types of reactions are presented in which the use of microstructured devices led to an increased process performance by applying Novel Process Windows. These examples were chosen to demonstrate how chemical reactions can benefit from the use of milli- and microstructured devices and how existing protocols can be changed toward process conditions hitherto not applicable in standard laboratory equipment. The used milli- and microstructured reactors can also offer advantages in other areas, for example, high-throughput screening of catalysts and better control of size distribution in a particle synthesis process by improved mixing, etc. The chemical industry is under continuous improvement. So, a lot of research is being done to synthesize high value chemicals, to optimize existing processes in view of process safety and energy consumption and to search for new routes to produce such chemicals. Leitmotifs of such undertakings are often sustainable development(1) and Green Chemistry(2).

Differential evolution (DE) is one of the novel evolutionary optimization methods used for solving the problems that consist of nondifferentiable, nonlinear and multi-objective functions. In this presented work, the classical DE technique and its various versions, such as opposition based on differential evolution (ODE), adaptive differential evolution (ADE), adaptive opposition based on differential evolution (AODE) which is an advanced version of ODE, are presented to determine the optimal feeding flow profile of an industrial scale fed-batch baker's yeast fermentation process. The main objective in any fed-batch fermentation process optimization is both to maximize the amount of the biomass at the end of the process and to minimize the ethanol formation during the process. Four different cases regarding the initial condition of the fermentation process were considered so as to evaluate the performances of proposed algorithms. Besides, two strategies of mutation and crossover operators, which are the most popular in DE's applications, were utilized for performance comparison tests. The influence of initial seed value, initial condition of the process, and both of the mutation and crossover strategies have been investigated for all the different classic, opposition-based, self-adaptive and adaptive opposition-based mechanisms. To demonstrate the performance comparison of the of DE's techniques, the experimental data collected from the fermentor with volume of 100 m(3) are presented with the optimization results obtained by using all the interested DE techniques for the same initial conditions., (2009 ISA. Published by Elsevier Ltd. All rights reserved.)

In this article, a new analytical method based on the direct synthesis approach is proposed for the design of a multi-loop proportional-integral (PI) controller. The proposed design method is aimed at achieving the desired closed-loop response for multiple-input, multiple-output (MIMO) processes with multiple time delays. The ideal multi-loop controller is firstly designed in terms of the relative gain and desired closed-loop transfer function. Then, the standard multi-loop PI controller is obtained by approximating the ideal multi-loop controller using the Maclaurin series expansion. The simulation study demonstrates the effectiveness of the proposed method for the design of multi-loop PI controllers. The multi-loop PI controller designed by the proposed method shows a fast, well-balanced, and robust response with the minimum integral absolute error (IAE)., (2009 ISA. Published by Elsevier Ltd. All rights reserved.)

The catalysis group of Solvias has its roots in the Central Research Laboratories of Ciba-Geigy. Since the early eighties its research has been focused on three areas of catalytic technology: heterogeneous hydrogenation, coupling catalysis, and enantioselective hydrogenation. Today, these are still the catalytic methods with the greatest industrial potential. In this overview a short description will be given how these methods have been developed further since the spin-off of Solvias in 1999. It will be discussed which strategies were successful and what the most important results have been in the first decade of Solvias.

In the present study, a new method is presented for estimation of lower flammability limit (LFL) of pure compounds. This method is based on a combination of a group contribution method and neural networks. The parameters of the model are the occurrences of a new collection of 105 functional groups. Basing on these 105 functional groups, a feed forward neural network is presented to estimate the LFL of pure compounds. The average absolute deviation error obtained over 1057 pure compounds is 4.62%. Therefore, the model is an accurate model and can be used to predict the LFL of a wide range of pure compounds.

Pure terphthalic acid (PTA) is produced by the oxidation of paraxylene in an oxidation reactor of a PTA plant. Since the reaction is exothermic, the temperature rises above 210 degrees C. Vapours formed in the reactor are passed through a series of heat exchangers and the cooled liquid is fed back to the reactor, which flows to the reactor by gravity. In one of the heat exchangers, improper flow distribution in the inlet and outlet pipelines was suspected. Maldistribution of flow in the heat exchanger was also suspected. Gamma scanning of the pipelines and a radiotracer experiment were carried out in the heat exchanger to study the malfunctioning. A specially fabricated pipe scanner was used to scan both 24in diameter and 16in diameter pipelines. From gamma scanning of the pipelines mostly on the bends, absence of the full bore flow of the liquid was observed. Presence of vapours along with the liquid could be obstructing the liquid flow, thereby causing the malfunctioning. A radiotracer experiment was also carried out to study the flow pattern in the heat exchanger. From the experiment, mean residence time of the heat exchanger was estimated as 470s, which theoretically should be about 102s. It indicated that the flow is decelerated in the heat exchanger because of the presence of vapour lock in the tube side.

The flow rate measurements of dual-phase pipe flow were conducted with a couple of sealed radioisotopes for the cross-correlation technology. The flow was produced in an acrylic tubing of which internal diameter is 8cm and into which pressurized nitrogen gas was periodically injected. Under the given conditions where the distance between two sources is four times of the diameter, N/S ratio ranges from 0.12 to 0.15 and the data sampling time is 4ms, the measured flow rates were estimated with the maximum relative error of 1.7%. From the subsequent experiments, it was proven that the closer the distance between the two sealed sources is, the higher the precision of measurement result is. It is anticipated that the industrial application of the technique for flow rate measurements in an in-service process can play an important role for monitoring multi-phase process media in petrochemical and refinery industries.

Operation of microbial electrolysis cells (MECs) without an ion exchange membrane could help to lower the construction costs while lowering the ohmic cell resistance and improving MEC conversion rates by minimizing the pH gradient between anode and cathode. In this research, we demonstrate that membraneless MECs with plain graphite can be operated for methane production without pH adjustment and that the ohmic cell resistance could be lowered with approximately 50% by removing the cation exchange membrane. As a result, the current production increased from 66 +/- 2 to 156 +/- 1 A m(-3) MEC by removing the membrane with an applied voltage of -0.8 V. Methane was the main energetic product despite continuous operation under carbonate-limited and slightly acidified conditions (pH 6.1-6.2). Our results suggest that continuous production of hydrogen in membraneless MECs will be challenging since methane production might not be avoided easily. The electrical energy invested was not always completely recovered under the form of an energy-rich biogas; however, our results indicate that membraneless MECs might be a viable polishing step for the treatment of the effluent of anaerobic digesters as methane was produced under low organic loading conditions and at room temperature.

A new sonoreactor technology is presented here which should give a decisive impulse to sonochemistry in various areas of chemical processing. These exclusive systems use high power converging acoustic waves in a tube to produce a relatively large volume confined acoustic cavitation zone in flowing liquid reagents under pressure. It is well known that numerous chemical reactions are strongly accelerated when they take place inside such a zone. The new cylindrical sonoreactors do not contaminate the processed liquids with erosion products as most other devices do since the cavitation zone is maintained away from the wall of the tube. The processing conditions can be widely varied with pressure, power, temperature, and flow rate. The processing capacity of the largest models may be up to several tons per hour, depending on the required cavitation energy per unit volume to produce the desired process enhancement, using an electric power input of about 50 kW.

In the present energy context, there is a growing interest for the fuel production from biomass. While the first generation of biofuels has shown its limits, a second generation appears that is based on the valorisation of the unused resources of lignocellulosic biomass. This could significantly increase the biofuels potential in France. Up to 40 % of the total needs of transport fuel could be covered. Among the processes under development, the Biomass to Liquid (BtL) process seems as an interesting route, able to be shortly implemented at an industrial scale. This process consists in producing liquid fuel (such as Diesel Fischer-Trospch) through a synthetic gas obtained by biomass gasification However R&D work is still needed to solve the remaining key issues of the process. These studies are performed in several laboratories in Europe, especially in Germany and in the Nordic countries, and also more recently in France, notably in the Commissariat à l'Energie Atomique.

A method for determination of metabisulfite and hydrosulfite in poultice and decolorant by isotachophoresis was developed. Metabisulfite and hydrosulfite are ionizable oxoanions of sulfur of similar character that can easily be oxidized to sulfates. To protect the analytes from oxidation the solid samples were dissolved in a 1% (w/v) solution of formaldehyde. Hydrosulfite and metabisulfite present in the samples were transformed by the reaction with formaldehyde to stable compounds, hydroxymethanesulfinate and hydroxymethanesulfonate that were determined isotachophoretically without any pretreatment except for sample filtering and degassing. A capillary of 0.4mm i.d. and 100mm effective length made of fluorinated ethylene-propylene copolymer was filled with an electrolyte system consisting of 10 mmol L(-1) HCl+11 mmol L(-1) imidazole, 0.15% (w/v) hydroxyethylcellulose, pH 6.0 (leading electrolyte) and 5 mmol L(-1) benzoic acid+6 mmol L(-1) imidazole, pH 6.5 (terminating electrolyte). Separation was performed at a driving current of 80 microA and for detection current was decreased to 30 microA. Using contactless conductivity detection, the calibration curves in the tested concentration range up to 2.5 mmol L(-1) were linear for both metabisulfite and hydrosulfite complexes. The concentration detection limits for metabisulfite and hydrosulfite were 2.9 and 3.4 micromol L(-1), respectively. For 1 mmol L(-1) concentration, values of R.S.D. (n=6) were 2.6% for hydrosulfite and 0.8% for metabisulfite. Isotachophoretic determination took about 20 min. The elaborated isotachophoretic procedure is simple to perform, sufficiently sensitive and accurate. In addition to this, low cost of analyses makes the method an alternative procedure to methods used so far for the determination of oxoanions of sulfur.

Controlling fugitive emissions from leaks in petrochemical industry process equipment now requires periodic monitoring of valves, flanges, pumps etc., typically on a quarterly basis. Previous studies have shown that over 90% of the reducible emissions come from approximately 0.1% of the components, i.e. the large leakers. A new, and more cost-effective approach for controlling these large leakers would entail more frequent monitoring of process equipment, allowing for the detection and repair of the highly leaking components that contribute the most to emissions. This approach has been called "Smart LDAR." New optical imaging instruments, which significantly reduce monitoring costs, are now available to implement such an alternative work practice. This work describes the determination of the leak detection sensitivity (equivalency threshold) that an optical imaging instrument must achieve to ensure that it will provide at least the equivalent emission control of the current leak detection and repair practice. Equivalency thresholds were developed for various monitoring intervals. The U.S. Environment Protection Agency's Monte Carlo simulation approach was used to perform the analysis and to demonstrate that optical imaging, which is capable of identifying all of the largest leakers, can provide better control of fugitive emissions.

The biodegradability of four novel diethanolamine derivative complexing agents was examined by using two biodegradation tests standardised by OECD (301B and 301F). Ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) were employed as reference substances. Biodegradation of the new complexing agents was studied both with unacclimated and acclimated inocula as well as by simulating wastewater treatment in sequencing batch reactors (SBRs). These new complexing agents were of technical grade, and therefore, the results are only indicative but these new compounds hold promise for use as complexing agents in the pulp and paper industry. The novel complexing agents were not readily biodegradable but they showed slight biodegradation. Around 10-30% degradation was found in the SBR where degradation was followed by measurement of concentration. Moreover the novel complexing agents did not have any negative impact on reactor performance as measured by chemical oxygen demand reduction. In the standardised biodegradation tests at best around 50% degradation was observed with the acclimated inoculum and in the prolonged test whereas EDTA and DTPA exhibited no biodegradation. The elevated degradation in acclimated sludge indicates that the water treatment plant microbes are capable of decomposing these molecules under favourable conditions. The total concentration of novel complexing agents decreased slightly during biodegradation tests, while the EDTA and DTPA concentrations remained stable.

A nonlinear adaptive control strategy is proposed for a binary batch distillation column. The hybrid control algorithm comprises a generic model controller (GMC) and a nonlinear adaptive state estimator (ASE). The adaptive observation scheme mainly estimates the imprecisely known parameters based on the available tray temperature measurements. The sensitivity of the proposed estimator is investigated with respect to the effect of initialization error, unmeasured disturbance and uncertainty. Then, a comparative study is carried out between the derived nonlinear GMC-ASE controller and a traditional proportional integral law in terms of set point tracking and disturbance rejection performance. The study also includes the effect of measurement noise and parametric uncertainty on the closed-loop performance. The proposed adaptive control algorithm is shown to be quite promising due to the exponential error convergence capability of the ASE estimator in addition to the high-quality control action provided by the GMC controller.

In order to produce only a pH-controlled solution without discharging any unused solution, this work has developed a continuous electrolytic system with an ion exchange membrane-equipped electrolyzer and a tank, called as a pH-adjustment reservoir, placed just in front of the electrolyzer, where as a target solution was fed into the pH-adjustment reservoir, a portion of the solution in the pH-adjustment reservoir was circulated through the cathodic or anodic chamber of the electrolyzer depending on the type of the ion exchange membrane used, and another portion of the solution in the pH-adjustment reservoir was discharged from the electrolytic system through the opposite electrode chamber with its pH being controlled. The internal circulation of the pH-adjustment reservoir solution through the anodic chamber in the case of using a cation exchange membrane and that through the cathodic chamber in the case of using an anion exchange membrane could make the solution, discharged from the other counter chamber, effectively acidic and basic, respectively. The phenomena of the pH being controlled in the system could be explained by the electro-migration of the ion species in the solution through the ion exchange membrane under a cell potential difference between the anode and the cathode and its consequently-occurring non-charge equilibriums and the electrolytic water-split reactions in the anodic and cathodic chambers.

A 1-1 stainless steel (SS) reactor with a glass bottom has been designed with symmetrically placed internals so that gas entrapment is completely avoided during bulk polymerization of methyl methacrylate (MMA). This reactor is instrumented and controlled using virtual instrumentation. The power consumed by a constant-speed stirrer motor is measured as a function of time which, along with the temperature history, can be used to infer the state (monomer conversion xm and weight average molecular weight Mw) of the viscous reaction mass. This study highlights the importance of symmetry in the design of the reactor, proposes a novel reactor design, and discusses in detail the temperature control configuration that can help track any temperature history. Some preliminary results are reported for bulk polymerization of MMA and a correlation developed for the stirrer power, which can be used for soft sensing.

Ion exchange, adsorption, and chromatography are examples of separation processes frequently used in today's biorefineries. The particular tasks for which these technologies can be successfully applied are highly influenced by capital cost and efficiency. There exists a potential for significantly increasing the efficiency of these processes whereas simultaneously decreasing their size and capital cost. This potential for process intensification can be realized with the use of engineered fractal equipment. The cost savings potential and the possibilities for broadening the use of fractal-based separation technologies in future biorefinery concepts is illustrated by examples of full-scale implementation in the sugar and sweetener industries.

Forschungszentrum Karlsruhe has developed a concept for the utilization of cereal straw and other thin-walled biomass with high ash content. The concept consists of a regional step (drying, chopping, flash-pyrolysis, and mixing) and a central one (pressurized entrained-flow gasification, gas cleaning, synthesis of fuel, and production of byproducts). The purpose of the regional plant is to prepare the biomass by minimizing its volume and producing a stable and safe storage and transport form. In the central gasifier, the pyrolysis products are converted into syngas. The syngas is tar-free and can be used for Fischer-Tropsch synthesis after gas cleaning.

Acoustic cavitation plays an important role in enhancing the reaction rate of chemical processes in sonochemical systems. However, quantification of cavitation intensity in sonochemical systems is generally limited to low frequency systems. In this study, an empirical determination of cavitation yield in high frequency ultrasound systems was performed by measuring the amount of iodine liberated from the oxidation of potassium iodide (KI) solution at 1.7 and 2.4 MHz. Experiments for determining cavitation were carried out at various solute (KI) concentrations under constant temperature, obtained by direct cooling of the solution and variable temperature conditions, in the absence of external cooling. Cavitation yield measurements, reported in this work, extend previously reported results and lend credence to the two step reaction pathway in high frequency systems. Additionally, the concentration of KI and temperature affect the cavitation yield of a system such that the iodine production is proportional to both conditions. It is proposed that direct cooling of sonicated KI solution may be advantageous for optimization of cavitation intensity in high frequency sonochemical reactors.

Abstract In the frame of the Petróleos Mexicanos Institutional Program for Sustainable Development, processes were evaluated in the manufacture operation of the petrochemical industry, with the purpose of reducing their ecological fingerprint. Thirteen cleaner production opportunities were registered in six process plants: ethylene oxide and glycols, acetaldehyde, ethylene, high density polyethylene, polypropylene switch and acrylonitrile, and 45 recommendations in the waste water treatment plant. Morelos is the second most important petrochemical complex in the Mexican and Latin American petrochemical industry. A tool was developed to obtain eco-efficiency indicators in operation processes, and as a result, potential savings were obtained based on best performance, as well as the integrated distribution of Sankey diagrams. Likewise, a mechanism of calculation to obtain economic savings based on the reduction of residues during the whole productive process is proposed. These improvement opportunities and recommendations will result in economic and environmental benefits minimising the use of water, efficient use of energy, raw materials and reducing residues from source, generating less environmental impacts during the process.

A nonlinear first principle model is developed for a laboratory-scaled multivariable chemical reactor rig in this paper and the on-line model predictive control (MPC) is implemented to the rig. The reactor has three variables-temperature, pH, and dissolved oxygen with nonlinear dynamics-and is therefore used as a pilot system for the biochemical industry. A nonlinear discrete-time model is derived for each of the three output variables and their model parameters are estimated from the real data using an adaptive optimization method. The developed model is used in a nonlinear MPC scheme. An accurate multistep-ahead prediction is obtained for MPC, where the extended Kalman filter is used to estimate system unknown states. The on-line control is implemented and a satisfactory tracking performance is achieved. The MPC is compared with three decentralized PID controllers and the advantage of the nonlinear MPC over the PID is clearly shown.

A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation unit data.

Computational fluid dynamics simulations were employed to compare performance of various designs of a pretreatment screw conveyor reactor. The reactor consisted of a vertical screw used to create cross flow between the upward conveying solids and the downward flow of acid. Simulations were performed with the original screw design and a modified design in which the upper flights of the screw were removed. Results of the simulations show visually that the modified design provided favorable plug flow behavior within the reactor. Pressure drop across the length of the reactor without the upper screws in place was predicted by the simulations to be 5 vs 40 kPa for the original design.

The CFD (computational fluid dynamics) technique is used to describe the mixing conditions in a pilot-scale FCC (forced-circulation crystallizer) and to study the impact of flow rate and aspect ratio on local flow conditions and RTD (residence-time distribution) in the crystallizer. The analysis adequately predicts the oscillating flow and two-phase (gas-liquid) interaction at the free surface. A comparison has been made between the CFD predictions and models of RTD. The results support the use of CFD methodology as an aid to optimization of commercial-scale FCC design.

A 785 nm laser dispersive Raman system was installed in a hazardous chemical production plant to monitor two reactors, a still, and a holding tank with measurement directly through sight glasses. Compositional information for several raw materials, intermediates, and products was obtained using partial least squares (PLS) calibrations. Discriminate analysis was used to exclude extremely poor spectra while including usable ones. Derivative/standard normal variate (SNV) treatment was found to be effective for correcting for background fluorescence and for large differences in spectral intensity. Final regression equations incorporated temperature fluctuations, occasional fluorescence, some sunlight effects, large intensity variations, and large compositional changes. Various installation problems were solved via data treatment or mechanical changes. The Raman system provides information for control of the process, resulting in cost savings and improved safety.

A new mathematical treatment of alarms that considers them as multi-variable interactions between process variables has provided the first-ever method to calculate values for alarm limits. This has resulted in substantial reductions in false alarms and hence in alarm annunciation rates in field trials. It has also unified alarm management, process control and product quality control into a single mathematical framework so that operations improvement and hence economic benefits are obtained at the same time as increased process safety. Additionally, an algorithm has been developed that advises what changes should be made to Manipulable process variables to clear an alarm. The multi-variable Best Operating Zone at the heart of the method is derived from existing historical data using equation-free methods. It does not require a first-principles process model or an expensive series of process identification experiments. Integral with the method is a new format Process Operator Display that uses only existing variables to fully describe the multi-variable operating space. This combination of features makes it an affordable and maintainable solution for small plants and single items of equipment as well as for the largest plants. In many cases, it also provides the justification for the investments about to be made or already made in process historian systems. Field Trials have been and are being conducted at IneosChlor and Mallinckrodt Chemicals, both in the UK, of the new geometric process control (GPC) method for improving the quality of both process operations and product by providing Process Alarms and Alerts of much high quality than ever before. The paper describes the methods used, including a simple visual method for Alarm Rationalisation that quickly delivers large sets of Consistent Alarm Limits, and the extension to full Alert Management with highlights from the Field Trials to indicate the overall effectiveness of the method in practice.

An explosion occurred at a polyvinyl chloride (PVC) resin manufacturing plant. The explosion originated at an atmospheric storage vessel when it received a slurry discharge from a suspension polymerization reactor. The pressure rise caused by the uncontrolled flashing of superheated liquid vinyl chloride resulted in the complete separation of the roof from the tank shell. A cloud of vinyl chloride vapor was released and ignited resulting in a vapor cloud explosion. The accident caused significant property damage but no serious injuries. An investigation was conducted to determine the causes of the accident. It was discovered that the facility had experienced numerous overpressure incidents in the atmospheric storage vessels used as slurry tanks. Many of these incidents resulted in modest structural damage to these slurry tanks. It was determined by Exponent that the rapid flashing of residual liquid monomer present in the product slurry stream caused the earlier overpressure incidents. The facility operator did not adequately investigate or document these prior overpressure events nor did it communicate their findings to the operating personnel. Thus, the hazard of flashing liquid vinyl chloride was not recognized. The overpressure protection for the slurry tanks was based on a combination of a venting system and a safety instrumentation system (SIS). The investigation determined that neither the venting system nor the SIS was adequate to protect the slurry tank from the worst credible overpressure scenario. Fundamentally, this is because the performance objectives of the venting system and SIS were not clearly defined and did not protect against the worst credible overpressure scenario. The lessons learned from this accident include: use prior incident data for recognizing process hazards; identify targets vulnerable to these hazards; explicitly define performance objectives for safeguards to protect against the worst credible overpressure scenario. The ultimate lesson learned here is that a liquid trapped under pressure above its normal boiling point represents an overpressure hazard. To avoid exceeding the design pressure of the receiving vessel, the superheated liquid must be discharged slowly so that the vapor production rate caused by flashing does not exceed the venting rate of the receiving vessel.

On the morning of 14 August 2002, a 1 in. transfer hose used in a rail tank car unloading operation at DPC Enterprises, near Festus, Missouri, catastrophically ruptured and initiated a sequence of events that led to the release of 48,000 pounds of chlorine--a toxic gas--into neighboring areas. The facility repackages bulk dry liquid chlorine into 1 ton containers and 150 pound cylinders for commercial, industrial, and municipal use in the St. Louis metropolitan area. Fortunately, the wind direction on the day of the release limited the effects of the chlorine plume on the surrounding community. However, 63 people sought hospital treatment due to exposure, and hundreds of others were affected by the release (the community was advised to shelter-in-place for 4 h, and traffic was halted on Interstate 55 for 1.5 h). The US Chemical Safety and Hazard Investigation Board (CSB) investigated this incident for the following reasons: This paper presents the lesson-learned from this incident to help prevent similar occurrences. This paper is based on US Chemical Safety and Hazard Investigation Board Report Number 2002-04-I-MO, which was approved by the Board on 1 May 2003. This paper has not been independently approved by the Board and is published for general informational purposes only. Every effort has been made to accurately present the contents of the Board-approved report in this paper. Any material in the paper that did not originate in the Board-approved report is solely the responsibility of the author and does not represent an official finding, conclusion, or position of the Board. A complete copy of the Board investigation report upon which this paper is based is available on the CSB website at "Completed Investigations."

Whereas the beta-lactam acylases are traditionally used for the hydrolytic processing of penicillin G and cephalosporin C, new and mutated acylases can be used for the hydrolysis of alternative fermentation products as well as for the synthesis of semisynthetic beta-lactam antibiotics. Three-dimensional structural analyses and site-directed mutagenesis studies have increased the understanding of the catalytic mechanism of these enzymes. The yield of hydrolysis and synthesis has been greatly improved by process design, including immobilization of the enzyme and the use of alternative reaction media. Significant advances have also been made in the resolution of racemic mixtures by means of stereoselective acylation/hydrolysis using beta-lactam acylases.

Glutaryl-7-aminocephalosporanic acid acylase (GA), an industrially relevant enzyme, has been immobilized onto very different supports, including glyoxyl agarose, heterofunctional epoxy Sepabeads, glutaraldehyde and cyanogen bromide (CNBr) activated supports. Immobilization onto amino-epoxy Sepabeads rendered the most thermo stable preparation of GA, with a half-life time eight times higher than the soluble enzyme, keeping 80% of the enzyme activity. Several parameters that affect the enzyme-support interaction (pH and incubation time) were studied. It was found that after immobilization onto amino-epoxy Sepabeads, incubation at alkaline pH and low temperature exerted dramatic stabilizing effects, increasing the half-life time of the derivative 130 times with respect to the soluble enzyme, while keeping unaltered its intrinsic activity. The loading capacity of the amino-epoxy Sepabeads proved to be very good with a maximum load of 62 mg of protein per g of support with 85 IU/g at 25 degrees C and 200 IU/g at 37 degrees C which makes it a biocatalyst of possible industrial application.

Accidents caused by domino effect are among the more severe that took place in the chemical and process industry. However, a well established and widely accepted methodology for the quantitative assessment of domino accidents contribution to industrial risk is still missing. Hence, available data on damage to process equipment caused by blast waves were revised in the framework of quantitative risk analysis, aiming at the quantitative assessment of domino effects caused by overpressure. Specific probit models were derived for several categories of process equipment and were compared to other literature approaches for the prediction of probability of damage of equipment loaded by overpressure. The results evidence the importance of using equipment-specific models for the probability of damage and equipment-specific damage threshold values, rather than general equipment correlation, which may lead to errors up to 500%.

A quantitative assessment of the contribution to industrial risk of domino effect due to overpressure was undertaken by using the damage probability models developed in part I. Two case studies derived from the actual lay-out of an oil refinery were analyzed. Individual and societal risk indexes were estimated both in the absence and in the presence of the domino effects caused by overpressure. An increase of individual risk up to an order of magnitude was found when considering domino effects.

Mechanochemistry is a possible route to synthesize calcium deficient hydroxyapatite (CDHA) with an expected molar calcium-to-phosphate (Ca/P) ratio +/-0.01. To optimize the experimental conditions of CDHA preparation from dicalcium phosphate dihydrate (DCPD) and calcium oxide by dry mechanosynthesis reaction, we performed the kinetic study varying some experimental parameters. This kinetic study was carried out with two different planetary ball mills (Retsch or Fritsch Instuments). Results obtained with the two mills led to the same conclusions although the values of the rate constants of DCPD disappearance and times for complete reaction were very different. Certainly, the origin of these differences was from the mills used, thus we investigated the influence of instrumental parameters such as the mass and the surface area of the balls or the rotation velocity on the mechanochemical reaction kinetics of DCPD with CaO. Results show that the DCPD reaction rate constant and the inverse of the time for complete disappearance of CaO both vary linearly with (i) the square of the rotation velocity, (ii) the square of eccentricity of the vial on the rotating disc and (iii) the product of the mass by the surface area of the balls. These observations comply with theoretical models developed for mechanical alloying. The consideration of these four parameters allows the transposition of experimental conditions from one mill to another or the comparison between results obtained with different planetary ball mills. These instrumental parameters have to be well described in papers concerning mechanochemistry or when grinding is an important stage in a process.

This paper discusses the object-oriented software design for an automatic blending system. By combining the advantages of a programmable logic controller (PLC) and an industrial control PC (ICPC), an automatic blending control system is developed for a chemical plant. The system structure and multithread-based communication approach are first presented in this paper. The overall software design issues, such as system requirements and functionalities, are then discussed in detail. Furthermore, by replacing the conventional dynamic link library (DLL) with virtual X device drivers (VxD's), a practical and cost-effective solution is provided to improve the robustness of the Windows platform-based automatic blending system in small- and medium-sized plants.

Glycosides are of commercial interest for industry in general and specifically for the pharmaceutical and food industry. Currently chemical preparation of glycosides will not meet EC food regulations, and therefore chemical preparation of glycosides is not applicable in the food industry. Thus, enzyme-catalyzed reactions are a good alternative. However, until now the low yields obtained by enzymatic methods prevent the production of glycosides on a commercial scale. Therefore, high yields should be established by a combination of optimum reaction conditions and continuous removal of the product. Unfortunately, a bioreactor for the commercial scale production of glycosides is not available. The aim of this article is to discuss the literature with respect to enzymatic production of glycosides and the design of an industrially viable bioreactor system.

This paper discusses a process for making a novel granular detergent with an interspersion particle comprising an anionic surfactant and a polymeric polycarboxalate. This process contains three steps to develop the interspersion particles with anionic surfactant and polymeric ploycarboxalate. The first step was to form a detergent particle by spray drying of an aqueous detergent slurry comprising anionic surfactant (liner alkyl benzene sulfonate) with the different levels of polymeric polycarboxalate. In the second step, the spray-dried granules were densified and ground by a roll compacter and a grinder. The ground particles were coated by nonionic and zeolite in a vertical batch type high shear mixer (third step). In this study, the feasibility to make better performance of granular detergent was discussed.