Modeling and analysis of high‐impact poly(propylene) production processes, 1. Effect of chemical poisoning on particle size distribution and gel formation

This work presents a simple model for a two‐stage process of high impact poly(propylene) (HIPP) production. The model predicts the bivariate distribution of particle size and polymer composition. It takes into account the effect of chemical poisoning on gel particle formation. The result shows that poisoning the solid catalyst is not an effective method for gel reduction. A better approach is to saturate the polymer particles with a co‐catalyst in reactor 1 and poison the co‐catalyst in reactor 2. It is also shown that the residence time distribution (RTD) of reactor 1 has a strong effect on the gel particle formation. A continuous reactor with narrow RTD is advantageous for gel reduction. The model provides some guidance for the analysis and design of the HIPP production process.     

Radon as a tracer to determine the mean residence times of groundwater in decontamination reactors

The groundwater at a former gasoline production site in Germany is heavily contaminated with aromatic hydrocarbons (mostly benzene) and is currently being treated in bioreactors under anaerobic conditions. To determine the reaction kinetics it is essential to know the mean residence time of the groundwater in these reactors. Most of the commonly used tracers (dyes and salts) did not give reliable results because of their interaction with the mineral matrix in the reactors. In this study radon (²²²Rn) dissolved in the groundwater is used as the tracer. The flow rate of groundwater through the reactors is 1 l/h. Over a period of 8 hours the radon-spiked groundwater was injected into the natural groundwater which has a very low radon concentration. The radon concentration of the discharged water is measured online at the reactor outlet. An increasing radon concentration at the reactor exit indicates the shortest residence time of the water. The time-dependent progress of the radon concentration provides detailed information about the flow behavior and residence times of water in the reactor.     

Size evolution of gold nanoparticles in a millifluidic reactor

The size evolution of gold nanoparticles in a millifluidic reactor is investigated using spatially resolved transmission electron microscopy (TEM). The experimental data is supported by numerical simulations, carried out to study the residence-time distribution (RTD) of tracers that have the same properties as Au ions. Size and size distribution of the particles within the channels are influenced by the mixing zones as well as the RTD. However, the Au nanoparticles obtained show a broader size distribution even at the shortest investigated residence time of 3.53 s, indicating that in addition to surface growth reaction kinetics also plays an important role. The comparison of time resolved particle growth within the millifluidic channel with flask-based reactions reveals that the particle size can be controlled better within millifluidic channels. Overall, the results indicate potential opportunities to utilize easy to fabricate millifluidic reactors for the synthesis of nanoparticles, as well as as for carrying out time resolved kinetic studies.     

Mean residence time of Markov processes for particle transport in fludized bed reactors

A new approach for studying the particle dynamics and RTD (residence time distribution) in processes is to formulate stochastic models. A common question to all models for RTD is whether Danckwerts’ law for mean residence time holds. In this paper we revisit a Markov process that has been proposed by Dehling et al. (1999) as a stochastic model for particle transport in fluidized bed reactors. Under the volumetric flow balance conditions, we deduce different boundary conditions at the entrance and the exit of the reactor, and in both discrete model and continuous model we show that processes satisfy Danckwerts’ law, stating that the mean residence time of particle transport in fluidized bed reactors equals V/v, where V denotes the volume of the reactor occupied by the fluid and v the volumetric inflow rate.     

A Monte Carlo Method to Quantify the Effect of Reactor Residence Time Distribution on Polyolefins Made with Heterogeneous Catalysts: Part I—Catalyst/Polymer Particle Size Distribution Effects

Polyolefins are commercially produced in continuous reactors that have a broad residence time distribution (RTD). Most of these polymers are made with heterogeneous catalysts that also have a particle size distribution (PSD). These are totally segregated systems, in which the catalyst/polymer particle can be seen as a microreactor operated in semibatch mode, where the reagents (olefins, hydrogen, etc.) are fed continuously to the catalyst/polymer particle, but no polymer particle can leave. The reactor RTD has a large influence on the PSD of the polymer particles leaving the reactor, as well as in polymer microstructure and properties, polymerization yield, and composition of reactor blends. This article proposes a Monte Carlo model that can describe how particle RTD in a single or a series of reactors can affect the PSD of polymer particles made under a variety of operation conditions. It is believed that this is the most flexible model ever proposed to model this phenomenon, and can be easily modified to track all properties of interest during polyolefin production in continuous reactors with heterogeneous catalysts.     

Determination of polonium-210 in phosphoric acid

Polonium-210 in phosphoric acid has been recognized as a significant source of alpha contamination of processed Si-wafers for memory devices of computer. In the present work, a convenient method was developed for the determination of trace²¹⁰Po in phosphoric acid of high purity. For the determination,²⁰⁹Po was used as a yield tracer. The present method consists of (1) addition of the tracer to 5 ml aliquot of phosphoric acid sample, (2) pH adjustment (to 2) of the sample solution to make up electrolytic solution, (3) electrodeposition for the simultaneous achievement of Po separation and preparation of counting source on stainless-steel disc, and (4) alpha-ray spectrometry. By the developed method, more than 95% of Po was separated from phosphoric acid sample onto counting disc. The minimum detectable radioactivity of²¹⁰Po in 5 ml of phosphoric acid was about 0.03 mBq by counting the electrodeposited alpha-activity for 10 days under a counting efficiency of ≈30%.     

Residence time distribution study in a pilot-scale gas–solid fluidized bed reactor using radiotracer technique

This paper describes a radiotracer study carried out to measure residence time distribution (RTD) of coal particles in a pilot-scale gas–solid fluidized bed reactor (FBR). Gold-198 labelled on coal particles was used as radiotracer. RTD measurements were conducted for selected operating conditions and mean residence times (MRTs) of the coal particles were determined. Gamma function model was used to simulate the measured RTD data and mixing of coal particles in the reactor was investigated. Based on the results, the performance of the air distributor used in the reactor was evaluated.     

Cleaning time and fate of phosphoric acid as conditioning agent on human dental enamel and dentin. An in vitro radiotracer study

In this study the cleaning time and fate of phosphoric acid on human dental enamel and dentin has been investigated, using the radioactive tracer technique with³²P as an indicator of phosphorus. Twenty seconds were found to be sufficient for cleaning the enamel from phosphoric acid, which is used for conditioning, and from formulations produced from its interaction with enamel. It was also found that dentin protection is necessary before conditioning with phosphoric acid due to the retention penetration of the latter through subsurface dentinal tubules. In addition, there seems to be an interaction between phosphoric acid and Ca(OH)₂ leading to the formation of a sparingly soluble compound.     

Crystal modification of calcium sulfate dihydrate in the presence of some surface-active agents

The effect of surface-active agents (surfactants), as additives, on the crystallization of gypsum was studied under conditions of the simulated dihydrate process of phosphoric acid production. Calcium hydrogen phosphate and sulfuric acid were mixed with dilute phosphoric acid at 80 degrees C, and the turbidity of the reaction mixture was measured at different time periods to determine the induction time of gypsum crystal formation. Two types of surfactants, namely, cetyltrimethylammonium bromide (CTAB) as a cationic surfactant and sodium dodecyl sulfate (SDS) as an anionic surfactant were added to investigate their effects on the crystallization of gypsum. Addition of CTAB decreased the induction time and increased the growth efficiency, while addition of SDS increased the induction time and decreased the growth efficiency compared with the baseline (without additives). The surface energy increased with CTAB and decreased with SDS compared with the baseline. The percentage of fine crystals decreased in the presence of CTAB and increased in the presence of SDS compared with the baseline. Gypsum morphology changed from needle-like in the absence of additives to tabular in the presence of CTAB.     

Comparison between the performance of an immobilized impinging jet stream reactor and a slurry impinging jet stream reactor for photocatalytic phenol degradation

A new immobilized photocatalytic impinging jet stream reactor was designed, and the influences of the effective parameters like jet flow rate, TiO₂ coating disc diameter, nozzle-to-disc distance, and initial concentration on phenol removal were investigated. The reactor was also used as a slurry reactor, and degradation efficiencies in both reactors were compared based on their catalyst loading. The results indicated that the slurry reactor has a higher degradation efficiency than the immobilized reactor at the same TiO₂ loading and other operational conditions. The slurry reactor needs to separate and recover the TiO₂ nanoparticles from the reaction medium which increases the overall process complexity and cost, while the immobilized reactor could be reused at least 4times without any significant decrease in removal efficiency. RTD result indicates that the tank in series model (N?=?5) could properly predict the reactors hydrodynamic behavior.     

On-line monitoring of the residence time distribution along a kneading block of a twin-screw extruder

An on-line Residence Time Distribution (RTD) measuring set-up that enables the characterisation of twin screw extruders at short axial increments is presented. It uses the light emission of a fluorescent tracer (perylene) to generate concentration versus time curves, which are then used to determine the usual RTD parameters, delay time, mean residence time and variance. The system is initially mounted on a rectangular die coupled to a single screw extruder, on-line and off-line measurements being directly contrasted. Then, the optical probe is positioned at several points along the axis of a modular co-rotating twin screw extruder, on-line and off-line data being again compared. Having gained confidence in the measuring technique, an experimental unit utilizing a transparent barrel is used to characterize the evolution of RTD along a kneading block of a twin screw extruder.     

Thermal studies to determine the accelerated ageing of flares

Summary Thermal analysis is an interesting technique to determine kinetic parameters of separate components, and also of a complete system to receive adequate information on the ageing process of pyrotechnic compositions. The investigated tracer is a tracking tracer of a Swiss missile. It is attached to a missile and produces during burning a red flame. The missile system is already in use for 15 years. Periodic inspections of the system take place every three years. These inspections, however only give information on the actual state of the tracer and not on the future state. The aim of this investigation is to predict the ageing behaviour of the tracer system to give additional information about the future use of the missile system. After two ageing profiles the tracer systems were tested on the test range at Armasuisse in Thun. The results of the testing show that an ageing period of 4 weeks at 60°C gives no changes in performance (light output and burning time). On the other side also a quite heavy ageing period of 4 weeks at 150°C was applied on tracer systems, which gives a dramatically change in burning time. The light output was even higher after this ageing profile, although the intensity changes a lot.     

Continuous flow techniques in organic synthesis

As part of the dramatic changes associated with the need for preparing compound libraries in pharmaceutical and agrochemical research laboratories, the search for new technologies that allow automation of synthetic processes has become one of the main topics. Despite this strong trend for automation high-throughput chemistry is still carried out in batches, whereas flow-through processes are rather restricted to production processes. This is far from understandable because the main advantages of that approach are facile automation, reproducibility, safety, and process reliability, because constant reaction parameters can be assured. Indeed, methods and technologies are missing that allow rapid transfer from the research level to process development without time-consuming adaptation and optimization of methods from the laboratory scale to production plant scale. Continuous-flow processes are considered as a universal lever to overcome these restrictions and, only recently, joint efforts between synthetic and polymer chemists and chemical engineers have resulted in the first continuous-flow devices and microreactors; these allow rapid preparation of compounds with minimum workup. Many of these approaches use immobilized reagents and catalysts, which are embedded in a structured flow-through reactor. It is generally accepted, that for achieving best reaction and kinetic parameters for convective-flow processes monolithic materials are ideally suited as solid phases or polymer supports. In addition, immobilization techniques have to be developed that allow facile regeneration of the active species in the reactor.     

Determination of uranium in phosphoric acid using neutron activation analysis

Phosphoric acid is generally obtained from an aqueous process starting with the reaction between phosphate rock and sulphuric acid. Due to their chemical similarity, uranium is usually associated with phosphate rock which during chemical processing is partitioned to phosphoric acid. Uranium determination in this matrix is a very important task because of its ingestion it could lead to radiological impact on the population. Therefore, a procedure was developed using an initial precipitation with calcium hydroxide and evaporation, followed by instrumental neutron activation analysis (INAA). The procedure was applied to analyse fourteen uranium enriched phosphoric acid samples.     

Resting Study of Tracer Experiment on Catalytic Wet Oxidation Reactor under Micro-gravity and Earth Gravity Conditions

The International Space Station（ISS） employs catalytic wet oxidation carried out in a Volatile Reactor Assembly （VRA） for water recycling. Previous earth gravity experiments show that the VRA is very effective at removing polar, low molecular weight organics. To compare the reactor performance under micro-gravity and Earth gravity conditions, a tracer study was performed on a space shuttle in 1999 by using 0.2% potassium carbonate as the chemical tracer. In this paper, the experimental data were analyzed and it is indicated that the reactor can be considered as a plug flow one under both micro-gravity and earth gravity experimental conditions. It has also been proved that dispersion is not important in the VRA reactor under the experimental conditions. Tracer retardation was observed in the experiments and it is most likely caused by catalyst adsorption. It is concluded that the following reasons may also have influence on the retardation of mean residence time ： （1） the liquid can be held by appurtenances, which will retard the mean residence time; （2） the pores can hold the tracer, which can also retard the mean residence time.     

An Integrated Approach toward NanoBRET Tracers for Analysis of GPCR Ligand Engagement

Gaining insight into the pharmacology of ligand engagement with G-protein coupled receptors (GPCRs) under biologically relevant conditions is vital to both drug discovery and basic research. NanoLuc-based bioluminescence resonance energy transfer (NanoBRET) monitoring competitive binding between fluorescent tracers and unmodified test compounds has emerged as a robust and sensitive method to quantify ligand engagement with specific GPCRs genetically fused to NanoLuc luciferase or the luminogenic HiBiT peptide. However, development of fluorescent tracers is often challenging and remains the principal bottleneck for this approach. One way to alleviate the burden of developing a specific tracer for each receptor is using promiscuous tracers, which is made possible by the intrinsic specificity of BRET. Here, we devised an integrated tracer discovery workflow that couples machine learning-guided in silico screening for scaffolds displaying promiscuous binding to GPCRs with a blend of synthetic strategies to rapidly generate multiple tracer candidates. Subsequently, these candidates were evaluated for binding in a NanoBRET ligand-engagement screen across a library of HiBiT-tagged GPCRs. Employing this workflow, we generated several promiscuous fluorescent tracers that can effectively engage multiple GPCRs, demonstrating the efficiency of this approach. We believe that this workflow has the potential to accelerate discovery of NanoBRET fluorescent tracers for GPCRs and other target classes.     

Identification of Non-Volatile Compounds Generated during Storage That Impact Flavor Stability of Ready-to-Drink Coffee

Coffee brew flavor is known to degrade during storage. Untargeted and targeted LC/MS flavoromics analysis was applied to identify chemical compounds generated during storage that impacted the flavor stability of ready-to-drink (RTD) coffee. MS chemical profiles for sixteen RTD coffee samples stored for 0, 1, 2, and 4 months at 30 °C were modeled against the sensory degree of difference (DOD) scores by orthogonal partial least squares (OPLS) with good fit and predictive ability. Five highly predictive untargeted chemical features positively correlated to DOD were subsequently identified as 3-caffeoylquinic acid, 4-caffeoylquinic acid, 5-caffeoylquinic acid, 3-O-feruloylquinic acid, and 5-O-feruloylquinic acid. The increase in the six acidic compounds during storage was confirmed by sensory recombination tests to significantly impact the flavor stability of RTD coffee during storage. A decrease in pH, rather than an increase in total acidity, was supported to impact the coffee flavor profile.     

Highly enantioselective organocatalytic Biginelli reaction

A series of binol- and H8-binol-based phosphoric acids have for the first time been evaluated for their ability to catalyze Biginelli reactions of aldehydes, thiourea or urea, and beta-keto esters. A new chiral phosphoric acid, derived from 3,3'-diphenyl-H8-binol, exhibited superior catalytic activity and enantioselectivity compared to its structural analogues, affording high enantioselectivities ranging from 85 to 97% ee with a wide scope of substrates. A metal-free preparation of optically active monastrol was achieved on the basis of the current process.     

Thermodynamic derivations of conditions for chemical equilibrium and of Onsager reciprocal relations for chemical reactors

For an isolated chemical reactor, we derive the conditions for chemical equilibrium in terms of either energy, volume, and amounts of constituents or temperature, pressure, and composition, with special emphasis on what is meant by temperature and chemical potentials as the system proceeds through nonequilibrium states towards stable chemical equilibrium. For nonequilibrium states, we give both analytical expressions and pictorial representations of the assumptions and implications underlying chemical dynamics models. In the vicinity of the chemical equilibrium state, we express the affinities of the chemical reactions, the reaction rates, and the rate of entropy generation as functions of the reaction coordinates and derive Onsager reciprocal relations without recourse to statistical fluctuations, time reversal, and the principle of microscopic reversibility.     

Radiotracer investigation in a rotary fluidized bioreactor

A rotary fluidized bioreactor (RFBR) designed for treatment of wastewater was required to be investigated for its hydrodynamic behaviour and validation of design. A radiotracer investigation was carried out to measure residence time distribution (RTD) of wastewater in the RFBR using ⁸²Br as a radiotracer. The radiotracer was instantaneously injected into the inlet feed line and monitored at the inlet and outlet of the reactor using collimated scintillation detectors connected to a data acquisition system. The measured RTD data was treated and simulated using a tanks-in-series model and model parameters i.e. number of tanks describing the degree of mixing was obtained. The results of the investigation showed no flow abnormalities and the reactor behaved as an ideal continuously stirred-tank reactor at all the operating conditions. Based on the results, the design of the reactor was validated.