Model development for semicontinuous production of ethylene and norbornene copolymers having uniform composition

Terminal and penultimate models for controlling copolymer composition distribution (CCD) in ethylene and norbornene (NB) copolymerization were developed by taking into account the variation of active site concentration with the initial comonomer ratio. The models were validated by batch polymerization experimental data. The terminal model gave better correlation with the composition data whereas the penultimate model had a better fit to the rate data. The terminal model was then used to design NB feeding policies in semicontinuous processes for targeted CCD profiles. Based on the model results, a series of ethylene‐NB copolymers with various NB contents were prepared. With the same NB content, the semicontinuous process produced a uniform composition, whereas the batch process yielded broad CCD. The batch samples had lower T_g values and broader transition ranges, even yielded crystalline materials. In contrast, the semicontinuous samples overcame the disadvantages. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Safe‐steering of batch process systems

This work considers the problem of controlling batch processes to achieve a desired final product quality subject to input constraints and faults in the control actuators. Specifically, faults are considered that cannot be handled via robust control approaches, and preclude the ability to reach the desired end‐point, necessitating fault‐rectification. A safe‐steering framework is developed to address the problem of determining how to utilize the functioning inputs during fault rectification to ensure that after fault‐rectification, the desired product properties can be reached upon batch termination. To this end, first a novel reverse‐time reachability region (we define the reverse time reachability region as the set of states from where the desired end point can be reached by batch termination) based MPC is formulated that reduces online computations, as well as provides a useful tool for handling faults. Next, a safe‐steering framework is developed that utilizes the reverse‐time reachability region based MPC in steering the state trajectory during fault rectification to enable (upon fault recovery) the achieving of the desired end point properties by batch termination. The proposed controller and safe‐steering framework are illustrated using a fed‐batch process example. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Determination of Mark–Houwink parameters of ethylene–norbornene copolymers and molecular characteristics estimation

Ethylene–norbornene copolymers (ENC) with ～ 50%, ～ 25% and ～ 15% norbornene (NB) fraction in a wide range of molecular weight were produced by metallocene catalysts. By coupling the gel permeation chromatography (GPC) with the intrinsic viscosity data in 1,2,4‐trichlorobenzene (TCB)at 150°C, the Mark–Houwink parameters of ENC were determined and compared with previous classical analysis using polyethylene's relative parameters. The results indicated that parameter K was considerably increased with decreasing NB fraction in ENC but parameter α was only increased slightly. Furthermore, the structure characteristics and correlative rheological parameters of resultant ENC were also calculated and discussed by the Stockmayer–Fixman analysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Performance evaluation of batch and unsteady state fed‐batch reactor operations for the production of a marine microbial surfactant

BACKGROUND: Biosurfactants are microbially derived surface‐active and amphipathic molecules produced by various microorganisms. These versatile biomolecules can find potential applications in food, cosmetics, petroleum recovery and biopharmaceutical industries. However, their commercial use is impeded by low yields and productivities in fermentation processes. Thus, an attempt was made to enhance product yield and process productivity by designing a fed‐batch mode reactor strategy. RESULTS: Biosurfactant (BS) production by a marine bacterium was performed in batch and fed‐batch modes of reactor operation in a 3.7 L fermenter. BS concentration of 4.61 ± 0.07 g L^?1 was achieved in batch mode after 22 h with minimum power input of 33.87 × 10³ W, resulting in maximum mixing efficiency. The volumetric oxygen flow rate (K_La) of the marine culture was about 0.08 s^?1. BS production was growth‐associated, as evident from fitting growth kinetics data into the Luedeking‐Piret model. An unsteady state fed batch (USFB) strategy was employed to enhance BS production. Glucose feeding was done at different flow rates ranging from 3.7 mL min^?1 (USFB‐I) to 10 mL min^?1 (USFB‐II). USFB‐I strategy resulted in a maximum biosurfactant yield of 6.2 g l^?1 with an increment of 35% of batch data. The kinetic parameters of USFB‐I were better than those from batch and USFB‐II. CONCLUSION: Comparative performance evaluation of batch and semi‐continuous reactor operations was accomplished. USFB‐I operation improved biosurfactant production by about 35% over batch mode. USFB‐I strategy was more kinetically favorable than batch and USFB‐II. © 2012 Society of Chemical Industry     

Real‐time control of a semi‐industrial fed‐batch evaporative crystallizer using different direct optimization strategies

This article presents a model‐based control approach for optimal operation of a seeded fed‐batch evaporative crystallizer. Various direct optimization strategies, namely, single shooting, multiple shooting, and simultaneous strategies, are used to examine real‐time implementation of the control approach on a semi‐industrial crystallizer. The dynamic optimizer utilizes a nonlinear moment model for on‐line computation of the optimal operating policy. An extended Luenberger‐type observer is designed to enable closed‐loop implementation of the dynamic optimizer. In addition, the observer estimates the unmeasured process variable, namely, the solute concentration, which is essential for the intended control application. The model‐based control approach aims to maximize the batch productivity, as satisfying the product quality requirements. Optimal control of crystal growth rate is the key to fulfill this objective. This is due to the close relation of the crystal growth rate to product attributes and batch productivity. The experimental results suggest that real‐time application of the control approach leads to a substantial increase, i.e., up to 30%, in the batch productivity. The reproducibility of batch runs with respect to the product crystal size distribution is achieved by thorough seeding. The simulation and experimental results indicate that the direct optimization strategies perform similarly in terms of optimal process operation. However, the single shooting strategy is computationally more expensive. © 2010 American Institute of Chemical Engineers AIChE J, 57: 1557–1569, 2011     

Application of nano‐zinc oxide master batch in polybutadiene styrene rubber system

The properties of nano‐zinc oxide master batch filled butadiene styrene rubber (SBR) systems were researched in comparison with those of common zinc oxide and nano‐zinc oxide filled systems. First, the nano‐zinc oxide master batch was prepared and the cure characteristics of three different kinds of zinc oxide filled SBR composites were studied; second, the mechanical properties and wear resistance were compared; then, the improved mechanical properties were confirmed by dynamic mechanical properties and transmission electron microscopy. Finally, the zinc oxide amount reducing mechanism was analyzed. Results show that nano‐zinc oxide master batch filled SBR system has better mechanical properties than those of nano‐zinc oxide and common zinc oxide filled systems, which is due to the improved dispersion by master batch mixing technology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 922–930, 2006     

A Mathematic Model for Direct Causticization of Na2CO3 with TiO2 in a Semi‐batch Reactor

A mathematic model was developed for direct causticization of sodium carbonate with titanium dioxide in a semi‐batch reactor. The model predictions of the titanate yield and pentatitanate yield showed a reasonable agreement with the experimental data from a pilot‐scale fluidized bed operating in semi‐batch mode. The rate constant of the present model was generally consistent with those obtained from the small‐scale batch experiments in the literature. A new rate constant considering carbonate conversion to pentatitanate was introduced. All the results provided support that the solid‐state direct causticization of sodium carbonate with titanium dioxide in a semi‐batch fluidized bed follows the shrinking‐core diffusion model.     

Integrated batch‐to‐batch and nonlinear model predictive control for polymorphic transformation in pharmaceutical crystallization

Polymorphism, a phenomenon in which a substance can have more than one crystal form, is a frequently encountered phenomenon in pharmaceutical compounds. Different polymorphs can have very different physical properties such as crystal shape, solubility, hardness, color, melting point, and chemical reactivity, so that it is important to ensure consistent production of the desired polymorph. In this study, an integrated batch‐to‐batch and nonlinear model predictive control (B2B‐NMPC) strategy based on a hybrid model is developed for the polymorphic transformation of L ‐glutamic acid from the metastable α‐form to the stable β‐form crystals. The hybrid model comprising of a nominal first‐principles model and a correction factor based on an updated PLS model is used to predict the process variables and final product quality. At each sampling instance during a batch, extended predictive self‐adaptive control (EPSAC) is employed as a NMPC technique to calculate the control action by using the current hybrid model as a predictor. At the end of the batch, the PLS model is updated by utilizing the measurements from the batch and the above procedure is repeated to obtain new control actions for the next batch. In a simulation study using a previously reported model for a polymorphic crystallization with experimentally determined parameters, the proposed B2B‐NMPC control strategy produces better performance, where it satisfies all the state constraints and produces faster and smoother convergence, than the standard batch‐to‐batch strategy. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Multivariate statistical process monitoring of batch‐to‐batch startups

In batch processes, multivariate statistical process monitoring (MSPM) plays an important role for ensuring process safety. However, despite many methods proposed, few of them can be applied to batch‐to‐batch startups. The reason is that, during the startup stage, process data are usually nonstationary and nonidentically distributed from batch to batch. In this article, the trajectory signal of each process variable is decomposed into a series of components corresponding to different frequencies, by adopting a nonparametric signal decomposition technique named ensemble empirical mode decomposition. Then, through instantaneous frequency calculation, these components can be divided into two groups. The first group reflects the long‐term trend between batches, which extracts the batch‐wise nonstationary drift information. The second group corresponds to the short‐term intrabatch variations. The variable trajectory signals reconstructed from the latter fulfills the requirements of conventional MSPM. The feasibility of the proposed method is illustrated using an injection molding process. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3719–3727, 2015     

Mechanical,vulcametric, and thermal properties of the different 5‐ethylidene 2‐norbornene content of ethylene‐propylene‐diene‐monomer vulcanized with different types and compositions of peroxides

Ethylene‐propylene‐diene‐monomer (EPDM) rubber is an important commercial polymer. The vulcanization process significantly changes its thermal, mechanical, and vulcametric properties. This study was carried out to find optimum formulation of EPDM composite for a better application in automotive industry. Sixteen EPDM polymer samples having different 5‐ethylidene 2‐norbornene (ENB) and ethylene contents were vulcanized with different types and compositions of peroxide and coagents. The mechanical and vulcametric properties of these samples were measured and compared. The type of peroxide, coagent, and EPDM grade affected the mechanical, thermal, and vulcametric properties of the EPDM rubber to some extend. Use of aromatic peroxide and coagent increased the thermal stability slightly. Mechanical properties were changed very slightly with the change of peroxide type for the same content of peroxide and coagent. Scorch time and cure time decreased with initial increase of the peroxide content. EPDM compound vulcanized with BBPIB peroxide and TAC/S coagent has higher cure time than EPDM compound vulcanized with DMBPHa peroxide and TMPTMA coagent. Coran method was used for the modeling of experimental data. Velocity constant for the formation of peroxide radical and polymer radical were found for each case. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Modeling and simulation of the sequencing batch reactor at a full‐scale municipal wastewater treatment plant

In this work, we attempted to modify the Activated Sludge Model No.3 and to simulate the performance of a full‐scale sequencing batch reactor (SBR) plant for municipal wastewater treatment. The long‐term dynamic data from the continuous operation of this SBR plant were simulated. The influent wastewater composition was characterized using batch measurements. After incorporating all the relevant processes, the sensitivity of the stoichiometric and kinetic coefficients for the model was thoroughly analyzed prior to the model calibration. The modified model was calibrated and validated with the data from both batch‐ and full‐scale experiments. Model predictions were compared with routine data in terms of chemical oxygen demand, NH₄⁺‐N and mixed liquid volatile suspended solids in the SBR, combined with batch experimental data under different conditions. The model predictions match the experimental results well, demonstrating that the model is appropriate to simulate the performance of a full‐scale wastewater treatment plant even operated under perturbation conditions. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Data‐driven model predictive quality control of batch processes

The problem of driving a batch process to a specified product quality using data‐driven model predictive control (MPC) is described. To address the problem of unavailability of online quality measurements, an inferential quality model, which relates the process conditions over the entire batch duration to the final quality, is required. The accuracy of this type of quality model, however, is sensitive to the prediction of the future batch behavior until batch termination. In this work, we handle this “missing data” problem by integrating a previously developed data‐driven modeling methodology, which combines multiple local linear models with an appropriate weighting function to describe nonlinearities, with the inferential model in a MPC framework. The key feature of this approach is that the causality and nonlinear relationships between the future inputs and outputs are accounted for in predicting the final quality and computing the manipulated input trajectory. The efficacy of the proposed predictive control design is illustrated via closed‐loop simulations of a nylon‐6,6 batch polymerization process with limited measurements. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2852–2861, 2013     

A novel approach to scheduling multipurpose batch plants using unit‐slots

Several models for scheduling multipurpose batch plants exist in the literature. The models using unit‐specific event points have shown better solution efficiency on various literature examples. This article presents a novel approach to scheduling multipurpose batch plants, which uses unit‐slots instead of process‐slots to manage shared resources such as material storage. We develop two slightly different models that are even more compact and simpler than that of Sundaramoorthy and Karimi, Chem Eng Sci. 2005;60:2679–2702. Although we focus on material as a shared resource, our multi‐grid approach rationalizes, generalizes, and improves the current multi‐grid approaches for scheduling with shared resources. Our models allow nonsimultaneous transfers of materials into and out of a batch. We show by an example that this flexibility can give better schedules than those from existing models in some cases. Furthermore, our approach uses fewer slots (event‐points) on some examples than even those required by the most recent unit‐specific event‐based model. Numerical evaluation using literature examples shows significant gains in solution efficiency from the use of unit‐slots except where the number of unit‐slots required for the optimal solution equals that of process slots. We also highlight the importance of constraint sequencing in GAMS implementation for evaluating mixed‐integer linear programming based scheduling models fairly. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Enhanced Production of Podophyllotoxin by Fed‐batch Cultivation of Podophyllum hexandrum

Podophyllum hexandrum (Indian May Apple) was successfully cultivated in a 3 L stirred tank bioreactor under low shear conditions in batch and fed‐batch modes of operation. A statistically optimized culture medium was used for the batch cultivation of Podophyllum hexandrum. Under optimum culture conditions of P. hexandrum, the batch culture showed a growth‐associated product formation with a maximum biomass of 21.4 g/L dry cell weight (DCW) basis and a podophyllotoxin production of 13.8 mg/L in 26 d. A mathematical model was developed to design the nutrient feeding strategies for a fed‐batch cultivation to prolong the productive log phase of cultivation. The fed‐batch cultivation was able to enhance the biomass and podophyllotoxin accumulation to 48 g/L (DCW basis) and 43.2 mg/L, respectively, in 60 d. The volumetric productivity of podophyllotoxin in fed‐batch cultivation was found to be 0.72 mg/(L. d) as opposed to 0.53 mg/(L. d) in batch cultivation under optimized culture conditions.     

Dynamic nonlinear batch process fault detection and identification based on two‐directional dynamic kernel slow feature analysis

The batch process generally covers high nonlinearity and two‐directional dynamics: time‐wise dynamics, which correspond to inherently time‐varying dynamics resulting from the slowly varying underlying driving forces within each batch duration; and batch‐wise dynamics, which are associated with different operating modes among different batches. However, most existing dynamic nonlinear monitoring methods cannot extract the slowly varying underlying driving forces of the nonlinear batch process and rarely tackle the batch‐wise dynamic characteristics among batch runs. In order to address these issues, a new monitoring scheme based on two‐directional dynamic kernel slow feature analysis (TDKSFA) is developed by combining kernel SFA with a global modelling strategy. In the TDKSFA method, kernel SFA is integrated with the ARMAX time series model to mine the nonlinear and time‐wise dynamic properties within a batch run due to its capability of extracting the slowly varying underlying driving forces. Furthermore, the global modelling strategy is presented to handle the batch‐wise dynamics among batches by calculating the total average kernel matrix of all training batches. After the slow features are extracted, Hotelling's T² and SPE statistics are built to detect faults. To solve the issue of fault variable nonlinear identification, a novel nonlinear contribution plot inspired by the pseudo‐sample variable projection trajectories in the TDKSFA model is further proposed to identify fault variables. Finally, the feasibility and effectiveness of the TDKSFA‐based fault diagnosis strategy is demonstrated through a numerical system and the penicillin fermentation process.     

A unified model of property integration for batch and continuous processes

This article aims to present a general model for synthesis of property‐based resource conservation networks. The proposed model is applicable to batch and continuous processes. Therein, the process systems are characterized by properties instead of composition that is found in most published works to date in the area of resource conservation. By treating continuous process as a special case of batch processes, both kinds of operations can be optimized with a unified model that is developed on the basis of a superstructure. The overall framework of property network is adopted, where material reuse/recycle, interception, and waste treatment are all taken into consideration. Apart from direct reuse/recycle, interception devices are employed to improve stream properties for further recovery, whereas effluent treatment is needed for compliance with environmental discharge limits. In addition, storage vessels are employed in batch processes to override intrinsic time constraint. Four case studies are solved to illustrate the proposed approach. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Integrating data‐based modeling and nonlinear control tools for batch process control

A data‐based multimodel approach is developed in this work for modeling batch systems in which multiple local linear models are identified using latent variable regression and combined using an appropriate weighting function that arises from fuzzy c‐means clustering. The resulting model is used to generate empirical reverse‐time reachability regions (RTRRs) (defined as the set of states from where the data‐based model can be driven inside a desired end‐point neighborhood of the system), which are subsequently incorporated in a predictive control design. Simulation results of a fed‐batch reactor system under proportional‐integral (PI) control and the proposed RTRR‐based design demonstrate the superior performance of the RTRR‐based design in both a fault‐free and faulty environment. The data‐based modeling methodology is then applied on a nylon‐6,6 batch polymerization process to design a trajectory tracking predictive controller. Closed‐loop simulation results illustrate the superior tracking performance of the proposed predictive controller over PI control. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Simultaneous saccharification and fermentation of sludge‐containing cassava mash for batch and repeated batch production of bioethanol by Saccharomyces cerevisiae CHFY0321

BACKGROUND: The aim of this study was to examine the repeated batch production of bioethanol from sludge‐containing cassava mash as starchy substrate by flocculating yeast to improve volumetric bioethanol productivity and to simplify the process of a pre‐culture system. RESULTS: For the repeated batch production of bioethanol using cassava mash, the optimal recycling volume ratio was found to be 5%. The repeated batch fermentation was completed within 36 h, while the batch fermentation was completed after 42 h. Volumetric productivity, final ethanol concentration, and ethanol yield were attained to 2.15 g L^?1 h^?1, 83.64 g L^?1, and 85.15%, respectively. Although cell accumulation in the repeated batch process is difficult due to the cassava mash, the repeated batch process using Saccharomyces cerevisiae CHFY0321 could exhibited 10‐fold higher initial viable cell number (1.7 × 10⁷ CFU mL^?1) than that of the batch process. CONCLUSION: The liquefied cassava powder was directly used for the repeated batch process without removal of sludge. Repeated batch bioethanol production by simultaneous saccharification and fermentation using self‐flocculating yeast could reduce process costs and accelerate commercial applications. This result was probably due in part to the effect of the initial viable cell density. Copyright © 2008 Society of Chemical Industry     

Miscibility,crystallization, and mechanical properties of poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate)/ poly(butylene succinate) blends

Naturally amorphous biopolyester poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P3/4HB) containing 21 mol % of 4HB was blended with semi‐crystal poly(butylene succinate) (PBS) with an aim to improve the properties of aliphatic polyesters. The effect of PBS contents on miscibility, thermal properties, crystallization kinetics, and mechanical property of the blends was evaluated by DSC, TGA, FTIR, wide‐angle X‐ray diffractometer (WAXD), Scanning Electron Microscope (SEM), and universal material testing machine. The thermal stability of P3/4HB was enhanced by blending with PBS. When PBS content is less than 30 wt %, the two polymers show better miscibility and their crystallization trend was enhanced by each other. The optimum mechanical properties were observed at the 5–10 wt % PBS blends. However, when the PBS content is more than 30 wt %, phase inversion happened. And the two polymers give lower miscibility and poor mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A Semi‐Batch Process for Nitroxide Mediated Radical Polymerization

Summary: A semi‐batch process using nitroxide mediated polymerization, was explored for the design of low molecular weight solvent‐borne coatings, typical of those used in the automotive industry. While living radical polymerization (LRP) offers many advantages in the control of polymer chain microstructure that may confer important physical and chemical property benefits to coatings, adapting LRP to a semi‐batch process poses significant challenges in the design and operation of the process. Using styrene monomer, various two‐component initiating systems (free radical initiator, 4‐hydroxy‐TEMPO) were studied to understand the effects of different initiators on the course of polymerization. In addition, an alkoxyamine was synthesized and used as the initiating source. The initiators Luperox 7M75 and Luperox 231 give higher polymerization rates and reasonable control over polymerization, while benzoyl peroxide (BPO), Vazo 67, and the alkoxyamine are less effective. The number of polymer chains in the final product is always less than the theoretical value, reflecting poor initiation efficiency, probably resulting from undesirable termination reactions that become important due to the nature of the semi‐batch process. Adding camphorsulfonic acid (CSA) or charging initiator concurrently with monomer during semi‐batch feed, can increase the polymerization rate while maintaining the living character of the polymerization. The copolymerization of styrene and butyl acrylate is also shown to exhibit living character.

Schematic representation of the exchange reaction to produce N‐TEMPO capped polymer chains.