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At least 415 records · Page 23

How exudates production along a phosphorus gradient influences mineral dissolution across contrasting soil development stages

Harnessing rhizosphere processes offers a valuable opportunity to optimize nutrient use efficiency in agroecosystems. In nutrient-limited soils, plants discharge part of photosynthate surplus via root exudation, including carboxylates, which may enhance mineral dissolution and nutrient mobilization. We aimed to assess how plant responses to nutrient limitation translated into changes in exudate profiles, and how these exudates, in turn, drive bioweathering processes across soils of contrasting mineralogy and weathering degree. We conducted a hydroponic experiment with Lupinus albus grown under five phosphorus (P) concentrations (5, 10, 20, 30, and 50 µM) over seven weeks. We measured plant biomass and root traits, performed a metabolomics analysis and quantified seven carboxylates in root exudates using gas chromatography-mass spectrometry. To assess bioweathering processes across contrasted soil domains, we conducted batch dissolution tests with exudates using three soil horizons—35 each with distinct physicochemical properties: enriched in organic matter, iron oxides, or primary silicates. At the intermediate level of P supply, shoot biomass was comparable to that under high P, but plants produced more root biomass and a higher total carboxylate exudation rate. Despite low carboxylate concentrations (<100 ppb), exudates promoted the dissolution of Ca, Mg, Si, Fe, P and K in all horizons. Yet, the degree of element released varied among horizons. These findings highlight the importance of root exudates in enhancing mineral dissolution, with effects dependent on soil physicochemical properties. The results suggest that managing agroecosystems under moderate nutrient limitation could be a sustainable strategy to increase root-to-shoot ratios, enhance bioweathering processes and nutrient release in soil solution.

Pollet, Sasha L.↗

Development of Spouting Bed Reactor for Reduction of Hematite to Magnetite (Final Report)

This project was designed to leverage both past and current technology development efforts and utilize the expertise of the National Energy Technology Laboratory (NETL) in a collaborative effort with SIOX for the development of a spouting bed reactor to produce magnetite from very fine hematite waste. More specifically, the effort involved the conversion of a steel manufacturing byproduct, iron oxide hematite (Fe 2 O 3 ), and reduces it chemically into a salable magnetite product applicable to a number of markets. SIOX previously operated a magnetite batch production facility based on a rotary kiln reactor process. Unfortunately, that process was both costly and inefficient, making it difficult to achieve desired economies, purity, and throughput levels. NETL’s technology, developed in this work, replaced the batch inefficient rotary kiln with a continuous spouting bed reactor capable of producing synthetic magnetite products. In the project, NETL was to develop the spouting bed for the SIOX application and SIOX was to construct and operate a fully integrated pilot scale demonstration plant. NETL successfully completed its tasks, but SIOX due to financial issues was not able to complete their tasks. They have chosen not to participate in this final report so for their tasks a short summary of NETL’s knowledge of their efforts is included.

36 MATERIALS SCIENCE↗

Solvent Recovery and Management at the Savannah River Site H-Canyon Facility

NIOWAVE, Inc. is a domestic supplier of medical and industrial isotopes from uranium and radium. The Savannah River National laboratory (SRNL) is currently providing support to NIOWAVE, which plans to deploy a superconducting electron linear accelerator (LINAC) to fission uranium for Mo-99 production without the need for a nuclear reactor or HEU. The uranium from the Mo-99 production targets will be purified using a modified PUREX (Plutonium Uranium Reduction Extraction) solvent extraction process to recover the uranium in the product stream. The uranium will then be precipitated as an oxalate which is calcined to U 3 O 8 to fabricate pellets for new Mo-99 targets. In previous support provided to NIOWAVE, the SRNL demonstrated a solvent washing process to remove degradation products from the tributyl phosphate (TBP) solvent used in the modified PUREX process under development for uranium recovery. To supplement this technology demonstration, NIOWAVE requested the SRNL to provide summary information on the solvent recovery and management activities which are used at the Savannah River Site (SRS) H-Canyon facility. An existing reference document for the reprocessing of irradiated HEU fuels at the SRS was used as the primary reference for the solvent management activities; although, other reference documents were used to provide supplementary information. The information provided includes a brief summary of the solvent degradation issues which have been observed in the H-Canyon solvent extraction cycles and resulting process safety concerns. The solvent recovery processes for the three cycles of solvent extraction used in the H-Canyon were subsequently described including the process equipment which consists of the continuous and batch solvent washers, pumps, and tanks. A final section is provided on the monitoring and analysis of solvent quality based on the previous work performed at the SRNL for NIOWAVE and past research and development activities performed to support the solvent extraction processes in both the SRS F-Canyon and H-Canyon facilities.

07 ISOTOPE AND RADIATION SOURCES↗

Flue gas CO 2 capture via electrochemically mediated amine regeneration: System design and performance

The electrochemically-mediated amine regeneration (EMAR) process uses electrons to modulate amine capacity to achieve CO2 separation from flue gas as an alternative to the traditional thermal regeneration process for CO2 capture. Here, the EMAR separation scheme is validated in a batch system designed to evaluate efficiency losses. Current and voltage responses of the electrochemical process were analyzed in a flow system operated continuously for up to 50 h. An isothermal EMAR system can achieve separation efficiencies above 80% from a 15% CO2 feed, which is representative of the CO2 composition in a flue gas. This bench scale continuous system can operate at 40–80 kJe/molCO2 with an amine regeneration of between 0.12 and 0.62 molCO2/molamine. The ability to separate CO2 at high electron utilization and moderate electrical energy consumption will prompt future research into optimization of the electrochemical separation unit to obtain long-term and stable operations for flue gas scrubbing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid design of top-performing metal-organic frameworks with qualitative representations of building blocks

Abstract Data-driven materials design often encounters challenges where systems possess qualitative (categorical) information. Specifically, representing Metal-organic frameworks (MOFs) through different building blocks poses a challenge for designers to incorporate qualitative information into design optimization, and leads to a combinatorial challenge, with large number of MOFs that could be explored. In this work, we integrated Latent Variable Gaussian Process (LVGP) and Multi-Objective Batch-Bayesian Optimization (MOBBO) to identify top-performing MOFs adaptively, autonomously, and efficiently. We showcased that our method (i) requires no specific physical descriptors and only uses building blocks that construct the MOFs for global optimization through qualitative representations, (ii) is application and property independent, and (iii) provides an interpretable model of building blocks with physical justification. By searching only ~1% of the design space, LVGP-MOBBO identified all MOFs on the Pareto front and 97% of the 50 top-performing designs for the CO 2 working capacity and CO 2 /N 2 selectivity properties.

36 MATERIALS SCIENCE↗

Biorenewable and circular polydiketoenamine plastics

Amid growing concerns over the human health and environmental impacts of plastic waste, the most promising solution would be to build a circular plastics economy where sustainability considerations dictate the full life cycle of plastics use including replacing petrochemicals with biorenewables. Here we show that by incorporating the polyketide triacetic acid lactone (TAL) in polydiketoenamines (PDK) we increase the working temperature of these circular plastics, opening the door wider to applications where circularity is urgently needed. By varying the number of carbons of TAL-derived monomers, both polymer properties and recycling efciency are afected. Simply using glucose as the main carbon source, we engineered a process for producing bioTAL under fed-batch fermentation. Furthermore, a systems analysis of this bioprocess under diferent scenarios quantifes the environmental and economic benefts of PDK plastics and the risks when implemented at an industrial scale, providing opportunities in biorenewable circularity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization Techniques for LiInSe{sub 2} Semiconducting Neutron Detector - Paper 55

As the world supply of helium continues to dwindle, alternatives to neutron detection have been a key focus area of radiation detection research. Solid-state neutron detectors are one possible alternative to the {sup 3}He detectors currently used for neutron detection when large detector areas are not required. Although {sup 6}Li and {sup 10}B are both also commonly used for neutron detection, neither has as high of a thermal cross section as {sup 3}He. The thermal cross sections for {sup 6}Li, {sup 10}B, and {sup 3}He are, respectively, 940 barns, 3840 barns, and 5330 barns. Both boron and helium are used in a gaseous form for neutron detection; however, there is no suitable gaseous form of lithium for neutron detection. Lithium is instead utilized in solid or liquid compounds for neutron detection. In this context, one area of interest is in the development of ternary A{sup I}B{sup III}C{sup IV} semiconductors comprised of isotopically-enriched lithium. Single crystal samples are being prepared through collaboration with the Y12 National Security Complex. This research focuses on the characterization of {sup 6}LiInSe{sub 2} (LISe) crystals, as well as on the development of prototype systems to assess the viability of using LISe crystals as a thermal neutron detector. Data to be obtained will provide previously untested physical parameters to facilitate growth optimization. Eventually, the refined crystals will be developed into solid-state, position-sensitive pixel detectors used for neutron imaging, among a wide array of possible applications including nuclear forensics. For the most part, the research team has been focused on mastering the detector fabrication processes, response tests on the first two batches of crystal samples, and the design of the first iteration detection system (Fig. 2). Response tests using alphas and neutrons have shown sensitivity to both particles. The first iteration detection system developed utilizes a 3-stage filter ladder of resistors and capacitors, similar to an ORTEC 142PC Preamplifier. Ideally, this ladder will reduce the noise associated with the high voltage power supply. The preamplifier is AC coupled to improve its counting rate capability (saturation), and critical components are on insulated posts. The custom circuit is housed in an aluminum box, and initial testing of the circuit has shown expected results. Investigation into further noise reduction is underway and will be the focus of the presented results. Upon completion and successful testing of the final detection system design, further development in spatial resolution and gamma/neutron discrimination will continue. (authors)

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Evaluating Liquid Waste Transfers and their Impacts to the SRS Tank Farm to Support Operations and Closure

The Liquid Waste (LW) contractor at the Savannah River Site, Savannah River Mission Completion (SRMC), supports the storage, processing, and safe disposition of legacy, radioactive liquid waste. The LW Tank Farms contain approximately 127 million liters (33.5 million gallons) of liquid waste within 43 active, underground waste tanks. To meet mission critical milestones for the closure of waste tanks and processing of 34 million liters (9 million gallons) of salt waste per year by the LW Salt Waste Processing Facility (SWPF), an increase in Tank Farm operations, including waste tank transfers, is required. Waste is compiled in salt and sludge batches in the Tank Farms and transferred to SWPF and the Defense Waste Processing Facility (DWPF) for treatment. All waste tank transfers, such as waste removal and batch compilation transfers, must be pre-evaluated to ensure Documented Safety Analysis (DSA) requirements are met via Evaluated Transfer Approval Forms (ETAFs). Facility conditions and configurations may change as a result of a waste transfer. These changes must be reflected in the Tank Farms Emergency Response Datasheet (ERD), which contains data utilized for operation and emergency situations.

Peterson, Shelby R.↗

Operation of Argonne's Liquid Salt-Liquid Metal Separation Testbed for U/TRU Product Processing

Argonne National Laboratory has constructed a liquid salt-liquid metal separation testbed for use in the development and advancement of cathode processing of U/TRU co‑deposits generated by pyroprocessing of used nuclear fuel. The U/TRU product recovered from the electrorefiner contains adhered and entrained salt that must be removed prior to consolidation of the U/TRU alloy for use in advanced reactor fuel fabrication. The bottom pour operation utilizes the low melting points of U/TRU co‑deposits and higher densities of molten metals compared to molten salts to separate and consolidate the U/TRU product. Argonne’s testbed is designed to support the development and optimization of bottom-pouring configurations for batch and semi-continuous operations, integration of process monitoring and control technologies, and determination of operational requirements for implementing in an industrial setting. Scoping tests were performed to demonstrate operational aspects of the testbed, including operation using single-pour spout and dual-pour spout configurations, effectiveness of salt containment and extent of salt vaporization, and the use of sensor probes to detect the location of the interface between the metal and salt phases during pouring. Recommendations for process optimization testing for further development of bottom pour processing to separate U/TRU alloys from adhered salt were made based on the results of scoping tests. Completing the recommended activities will increase the technical readiness level (TRL) of the liquid salt-liquid metal separation operation and consolidation of U/TRU alloys to support industrialization of pyroprocessing.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Numerical simulation of mold filling water blown polyurethane foams: Effects of sequential pour

Batch molding of polyurethane foams is a widely used processing technique to produce crosslinked cellular structures which form to the shape of the mold. For water-blown polyurethane foams, water is reacted to form gaseous carbon dioxide resulting in a foam which expands to fill the mold completely. Batch molding typically requires an operator to coat the surface of a mold, introducing a significant lag time during the filling stage where significant asymmetric volume change can occur. The purpose of this work is to show, through simulations, that this lag time is significant when predicting flow profiles and part quality. When the mold geometry is complex enough to force bifurcation of the flow, simulations incorporating various filling lag times predicted significantly different locations of knit or weld lines where the flow fronts meet. Current simulation techniques, which assume the filling stage occurs instantaneously, are unable to predict variations in weld line locations. The introduction of a lag time, referred to herein as sequential pour, was achieved through user-defined modules incorporated into Ansys Fluent software.

36 MATERIALS SCIENCE↗

Scalable, two–stage, autoinduction of recombinant protein expression in E. coli utilizing phosphate depletion

We report the scalable production of recombinant proteins in Escherichia coli, reliant on tightly controlled autoinduction, triggered by phosphate depletion in the stationary phase. The method, reliant on engineered strains and plasmids, enables improved protein expression across scales. Expression levels using this approach have reached as high as 55% of the total cellular protein. The initial use of the method in instrumented fed–batch fermentations enables cell densities of ~30 gCDW/L and protein titers up to 8.1 ± 0.7 g/L (~270 mg/gCDW). The process has also been adapted to an optimized autoinduction media, enabling routine batch production at culture volumes of 20 μl (384–well plates), 100 μl (96–well plates), 20 ml, and 100 ml. In batch cultures, cell densities routinely reach ~5–7 gCDW/L, offering protein titers above 2 g/L. Here, the methodology has been validated with a set of diverse heterologous proteins and is of general use for the facile optimization of routine protein expression from high throughput screens to fed–batch fermentation.

59 BASIC BIOLOGICAL SCIENCES↗

Summary Report for the Evaluation of Current QA Processes Within the FRMAC FAL and EPA MERL.

The Federal Radiological Monitoring and Assessment Center (FRMAC) relies on accurate and defensible analytical laboratory data to support its mission. Therefore, FRMAC must ensure that the environmental analytical laboratories providing analytical services maintain an ongoing capability to provide accurate analytical results to DOE. It is undeniable that the more Quality Assurance (QA) and Quality Control (QC) measures required of the laboratory, the less resources that are available for analysis of response samples. Being that QA and QC measures in general are understood to comprise a major effort related to a laboratory’s operations, requirements should only be considered if they are deemed “value-added” for the FRMAC mission. This report provides observations of areas for improvement and potential interoperability opportunities in the areas of Batch Quality Control Requirements, Written Communications, Data Review Processes, Data Reporting Processes, along with the lessons learned as they apply to items in the early phase of a response that will be critical for developing a more efficient, integrated response for future interactions between the FRMAC and EPA assets.

61 RADIATION PROTECTION AND DOSIMETRY↗

Enhanced Light Outcoupling from OLEDs Fabricated on Novel Low-Cost Patterned Plastic Substrates of Varying Periodicity

OLEDs continue to make strides in display applications, but their commercial utilization in solid-state lighting (SSL) is lagging. An ongoing challenge, in particular for manufacturing, is the need for enhanced efficiency and hence the necessity to increase in an inexpensive approach the extraction of the light generated inside the OLED into the forward (viewing) hemisphere. In conventional OLEDs fabricated on a transparent flat anode coated on glass, the external quantum efficiency (EQE) is only ~20%. About 50% of the light is lost to internal waveguiding in the high refractive index (RI) organic + ITO anode layers and to surface plasmon polaritons (SPPs) at the organic/metal cathode interface. Another ~30% of the light is externally waveguided in the substrate to its edges. While extraction of the externally waveguided light is commonly addressed by adding a microlens array (MLA) or a scattering layer at the substrate’s air-side, light outcoupling increases by only ~1.6-1.7x (vs up to 2.5x in improving from ~20% to ~50%). The use of a hemispherical lens or an index matching fluid (IMF) at the substrate/photodetector (PD) interface increases the outcoupling by at least 2x; these approaches however, are not viable industrially, and even a MLA is sometimes undesirable due to its non-planar, scattering structure. In multi-stack tandem OLEDs, where the metal cathode is far from the emitting zone(s), the impact of photons loss to SPPs decreases. Our project addressed the ~50% loss to the internally waveguided light and SPPs. We evaluated OLEDs fabricated on patterned or planarized plastic substrates manufactured in a cost-effective approach compatible with a roll-to-roll (R2R) process. The OLEDs were either (i) patterned to various degrees depending on the pitch a and height or depth h of the pattern features or (ii) planar, with a pattern buried under a flat high RI planarization layer. We demonstrated that the outcoupling from green patterned OLEDs reaches ~50% by mitigating plasmon–related loss and internal waveguiding, even without the addition of a MLA, a hemispherical lens, or IMF. Simulations conducted in parallel with the experimental effort demonstrated how diffraction by conformally corrugated OLEDs increases the outcoupling to >60%. Structures with varying pitch values were also simulated indicating that combining domains of varying pitch could increase outcoupling to 55-60%. Experimentally, we additionally assessed the role a and h in determining not only the OLED efficiencies, but also their structural properties, i.e., the uniformity and conformality throughout the OLED stack. As planar OLEDs are preferred over corrugated devices, we studied different patterns in plastic substrates that were planarized by a high RI formulation. Planar green OLEDs on such structures showed enhanced efficiencies with EQEs larger than 60% with the addition of an IMF (to extract the substrate mode) at the substrate/Si PD interface. White OLEDs showed EQEs of 45.5%. Plastic substrates are currently less attractive than glass substrates due to drawbacks such as permeability to water vapor and oxygen, and in some cases thermal instability. Plastic substrates however, are flexible and easy to handle unlike thin flexible glass, and once transparent thin barrier films are available, they will become more attractive; they are already of interest in medical applications. Importantly, as it is easy to generate various patterns in different plastic materials, they provide excellent means for assessing and optimizing enhancing extracting structures. Such structures can also be transferred to glass substrates with some process modifications. The technical effectiveness and economic feasibility of the project lie in the patterning of the extracting plastic substrates in an approach that is scalable to R2R manufacturing. R2R processes are of drastically lower-cost than batch or single-unit fabrication. The patterned plastic can be a part of an integrated substrate either plastic or glass, which includes also a MLA or a planar layer with embedded scattering particles, as well as a conductive metal mesh/electrode design. SSL is environmentally-friendly and as OLED SSL becomes more efficient it will reduce electricity consumption, and hence lighting cost, as well as produce less expensive attractive lighting fixtures. Our university-industry collaboration is hence of major benefit to the public as it demonstrates the feasibility of manufacturing optimized extracting substrates for highly efficient OLEDs for SSL in a future R2R process, which would drastically reduce the manufacturing cost and increase production in the USA. Moreover, newly developed methods by our team allow low-cost roll manufactured substrates to be transferred to flexible or rigid glass substrates, which solves the plastic substrate barrier issues, and when combined with device encapsulation will increase the OLEDs’ environmental stability.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Integration of SWPF into the DWPF Flowsheet: Gap Analysis and Test Matrix Development

Based on Revision 19 of the High Level Waste (HLW) System Plan, it is anticipated that the Salt Waste Processing Facility (SWPF) will be integrated into the Defense Waste Processing Facility (DWPF) flowsheet in October 2018 (or with Sludge Batch 11 (SB11)). Given that, Savannah River Remediation (SRR) has requested a technical basis be developed that validates the current Product Composition Control System (PCCS) models for use during the processing of the SWPF-based coupled flowsheet or that leads to the refinements of or modifications to the models that are needed so that the models may be used during the processing of the SWPF-based coupled flowsheet. To support this objective, Savannah River National Laboratory (SRNL) has completed three key interim activities prior to validation of the current or development of refined PCCS models over the anticipated glass composition region for SWPF processing. These three key activities include: (1) defining the glass compositional region over which SWPF is anticipated to be processed, (2) comparing the current PCCS model validation ranges to the SWPF glass compositional region from which compositional gaps can be identified, and (3) developing a test matrix to cover the compositional gaps.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Solid phase characterization and transformation of illite mineral with gas-phase ammonia treatment

In situ remediation applications of ammonia (NH 3 ) gas have potential for sequestration of subsurface contamination. Ammonia gas injections initially increase the pore water pH leading to mineral dissolution followed by formation of secondary precipitates as the pH is neutralized. However, there is a lack of understanding of fundamental alteration processes due to NH 3 treatment. In these batch studies, phyllosilicate minerals (illite and montmorillonite) were exposed to NH 3 gas with subsequent aeration to simulate in situ remediation. Following treatments, solids were characterized using a variety of techniques, including X-ray diffraction, N 2 adsorption-desorption analysis for surface area, Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), and microscopy methods to investigate physicochemical transformations. The results of this study indicate that, at high pH, the clays are altered as observed by differences in morphology and particle size via microscopy. However, the two clays interact differently with NH 3 . While montmorillonite interlayers collapsed due to intercalation, illite layers were unaffected as confirmed by FTIR analysis. Further, structural changes in silicate ([SiO 4 ] n- ) and aluminol (Al-OH) groups were identified by NMR and FTIR. This research showed that mineral alteration processes occur during and after NH 3 gas treatment which may be used to remove radionuclides from the aqueous phase through sorption, co-precipitation, and coating with secondary phyllosilicate alteration products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deployment of large tank monosodium titanate strike to increase salt processing at the Savannah river site - 15115

The treatment of high level waste (HLW) salt solutions using the Actinide Removal Process (ARP) and Modular Caustic Side Solvent Extraction Unit (MCU) began at Savannah River Site (SRS) in 2008. Since that time, over 6 million gallons of liquid HLW have been treated and the resulting low level waste (LLW) effluent immobilized in cementitious grout at salt-stone. In addition to the continued stabilization of liquid HLW, operating experience from the ARP/MCU facilities has also been valuable in considering the design and construction of the Salt Waste Processing Facility (SWPF) which will utilize similar unit operations on a much larger scale. ARP removes actinides by contacting waste with monosodium titanate (MST) which is a solid adsorbent for soluble strontium and actinides. Once the sorption reaction is complete, the MST solids are separated from salt solution via ultrafiltration through a crossflow filter. The throughput of initial operations of ARP/MCU was limited by the flowrate through the extraction process. However, after the implementation of a new solvent flowsheet, filtration of MST will be the rate limiting step in salt processing. For the entirety of ARP/MCU operation, Savannah River Remediation (SRR) has sought to improve process efficiency and performance through optimization and modification of the original facility design. These efforts have resulted in a best-single-year throughput of 4.9 million liters of decontaminated salt solution. In keeping with these practices, SRR recently initiated a project to improve filtration throughput by relocating the MST strike from small batches immediately upstream of the filtration unit to the underground waste tank used to batch and store salt solution feed for ARP/MCU. This process change will allow the bulk of MST solids to decant in the waste tank prior to filtration which should improve both the nominal operational filter flux as well as the achieved utility of filter operation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of a continuous synthesis process for carbamazepine using validated in-line Raman spectroscopy and kinetic modelling for disturbance simulation

Mitigation of failure modes in the continuous synthesis (CS) of a drug substance (DS) has the potential to widen the adoption of continuous manufacturing (CM) technologies by the pharmaceutical industry. Here, this work demonstrates the development of a robust continuous process for the synthesis of carbamazepine (CBZ), an essential medicine as per the World Health Organization (WHO), facilitated by kinetic modelling and monitored by in-line Raman spectroscopy. Accurate kinetic modelling and the use of validated process analytical technology (PAT) models for quantitative measurement were found to play an important role in developing CS of drug substances. Kinetic data for the formation of CBZ from iminostilbene (ISB) were collected by batch reaction sampling and high-performance liquid chromatography (HPLC) analysis. A non-linear solver and iterative method was applied to determine two sets of Arrhenius parameters simultaneously for the reaction system by minimizing the standard error of the model fit. The start-up and dynamic equilibrium stages for the CS of CBZ using a continuous stirred tank reactor (CSTR) were modelled based on the batch kinetic data and employed to optimize conversion and simulate process disturbances. An in-line Raman spectroscopy method was successfully developed, validated, and integrated to determine the concentrations of CBZ and ISB within the operating range for the CS. The CS kinetic model was evaluated experimentally from startup to dynamic equilibrium over 10 residence times with monitoring by HPLC and in-line Raman spectroscopy. The developed kinetic model in tandem with in-line Raman spectroscopy successfully predicted disturbances due to changes in process variables and can serve as a useful tool in the future design of advanced process control strategies for the continuous synthesis of CBZ.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗