High-throughput Reactor System Research Articles

Discovery and Synthesis Optimization of Isoreticular Al(III) Phosphonate-Based Metal-Organic Framework Compounds Using High-Throughput Methods.

High-throughput (HT) methods are an important tool for the fast and efficient screening of synthesis parameters and the discovery of new materials. This manuscript describes the synthesis of metal-organic frameworks (MOFs) from solution using an HT reactor system, resulting in the discovery of various phosphonate-based MOFs of the composition [Al2H12-x(PMP)3]Clx∙6H2O (H4PMP = N,N '-piperazine bis(methylenephosphonic acid)) for x = 4, 6, denoted as Al-CAU-60-xHCl, containing trivalent aluminum ions. This was accomplished under solvothermal reaction conditions by systematically screening the impact of the molar ratio of the linker to the metal and the pH of the reaction mixture on the product formation. The protocol for the HT investigation includes six steps: a) synthesis planning (DOE = design ofexperiment) within the HT methodology, b) dosing and working with in-house developed HT reactors, c) solvothermal synthesis, d) synthesis workup using in-house developed filtration blocks, e) characterization by HT powder X-ray diffraction, and f) evaluation of the data. The HT methodology was first used to study the influence of acidity on the product formation, leading to the discovery of Al-CAU-60∙xHCl (x = 4 or 6).

Water-gas shift of reformate streams over mono-metallic PGM catalysts

Mono-metallic Pt and Rh catalysts supported on both CeO2 and TiO2 were prepared and tested for water-gas shift activity in a Flowrence, high throughput reactor system. The feed composition mimicked a typical fuel processor, steam methane reformer outlet stream. The Pt/CeO2 catalyst showed the best metal activity of ∼3.8 E-07 moles CO converted·gPt-1 s-1, at a Pt loading of 0.5 wt%, activity decreasing with increasing metal loading. Furthermore, the Pt/CeO2 catalyst produced almost no methane while the Rh based catalysts led to substantial methanation.

Exploring the hydraulic fracturing parameter space: a novel high-pressure, high-throughput reactor system for investigating subsurface chemical transformations.

Hydraulic fracturing coupled with horizontal drilling (HDHF) involves the deep-well injection of a fracturing fluid composed of diverse and numerous chemical additives designed to facilitate the release and collection of natural gas from shale plays. Analyses of flowback wastewaters have revealed organic contamination from both geogenic and anthropogenic sources. The additional detections of undisclosed halogenated chemicals suggest unintended in situ transformation of reactive additives, but the formation pathways for these are unclear in subsurface brines. To develop an efficient experimental framework for investigating the complex shale-well parameter space, we have reviewed and synthesized geospatial well data detailing temperature, pressure, pH, and halide ion values as well as industrial chemical disclosure and concentration data. Our findings showed subsurface conditions can reach pressures up to 4500 psi (310 bars) and temperatures up to 95 °C, while at least 588 unique chemicals have been disclosed by industry, including reactive oxidants and acids. Given the extreme conditions necessary to simulate the subsurface, we briefly highlighted existing geochemical reactor systems rated to the necessary pressures and temperatures, identifying throughput as a key limitation. In response, we designed and developed a custom reactor system capable of achieving 5000 psi (345 bars) and 90 °C at low cost with 15 individual reactors that are readily turned over. To demonstrate the system's throughput, we simultaneously tested 12 disclosed HDHF chemicals against a radical initiator compound in simulated subsurface conditions, ruling out a dozen potential transformation pathways in a single experiment. This review outlines the dynamic and diverse parameter range experienced by HDHF chemical additives and provides an optimized framework and novel reactor system for the methodical study of subsurface transformation pathways. Ultimately, enabling such studies will provide urgently needed clarity for water treatment downstream or releases to the environment.

A high-throughput reactor system for optimization of Mo–V–Nb mixed oxide catalyst composition in ethane ODH

75 Mo–V–Nb mixed oxide catalysts with a broad range of compositions were tested using a high-throughput reactor in order to optimize the composition for the ethane oxidative dehydrogenation reaction.

Application of a Simultaneous TGA-DSC Thermal Analysis System for High-Throughput Screening of Catalytic Activity

We present here the use of a simultaneous TGA/DSC thermal analyzer as a high-throughput reactor system to measure after calibration the heat of reaction and therefore the catalytic activity of heterogeneous catalysts in a fast, reliable and reproducible manner. By coupling the gas outlet of the analyzer with a mass spectrometer via a heated capillary additional data can be acquired. As a test reaction the oxidation of carbon monoxide with synthetic air, using Hopcalite and several transition and noble metals as catalysts, was chosen. The setup presented allows the rapid sequential screening of about 70 catalysts per day.

High-Throughput Screening of Catalytic Materials for JP-8 Fuel Cracking to Liquefied Petroleum Gas

ABSTRACTA high-throughput methodology is applied for the discovery and optimization of novel catalyst formulations to convert readily available hydrocarbon-based JP-8 fuel directly into a lighter hydrocarbon product suitable for portable power applications utilizing LPG-powered fuel cells. In addition to catalytic cracking challenges, JP-8 cracking poses other challenges including high sulfur content (up to 3,000 ppmw) and significant concentration of aromatics, which are precursors to coking. An existing 16-channel high-throughput reactor system was modified for the JP-8 catalytic cracking studies. The catalyst support material was of primary importance in determining cracking activity. Alumina-based catalytic materials demonstrate the greatest activity for conversion of JP-8 to LPG during catalytic cracking at reactor temperatures above 600°C. This is attributed to the importance of acidic reaction sites within the structure of the catalytic support. The addition of noble metals to the alumina-based materials does not yield significant improvements in JP-8 conversion.

The ammonia selective catalytic reduction activity of copper-exchanged small-pore zeolites

The NH3-SCR activity of the small-pore zeolites, Cu-SSZ-13, Cu-SSZ-16, and Cu-SAPO-34, is investigated using a high-throughput reactor system. These copper exchanged small-pore zeolites have high SCR activity between 150 and 500°C and are shown to be much more hydrothermally stable than the medium-pore zeolite, Cu-ZSM-5. The degree of copper exchange, the dimensionality of the framework, and heteroatom framework substitution all impact the SCR activity and hydrothermal stability of the materials. Of the small-pore zeolites tested, Cu-SSZ-13 and Cu-SAPO-34 display superior SCR performance, both before and after high-temperature hydrothermal treatment.

High-Throughput Parallel Reactor System for Propylene Oxidation Catalyst Investigation

A high-throughput reactor system was designed for catalyst testing, which includes two important sections: the gas flow splitters and the parallel reactor. Each gas flow splitter could split one gas stream to 64 streams (8 x 8). The current system has two gas splitters that could feed two kinds of gases (from mass flow controllers) to a 64-channel (8 x 8) parallel fixed-bed reactor. The reactor is composed of tube connectors, a reactor tube array, a heating block, a product collector, and a temperature controller. The reactor system could test 64 catalysts simultaneously and give results, which are comparable with a regular single-channel microreactor. For the purpose of verifying the validity of the reactor system, propylene oxidation to prepare acrolein was used as the probing reaction. In order to analyze the reaction products, a high-throughput colorimetric diffusion-reflection imaging method was developed for the analysis of acrolein. By comparing the results from colorimetric diffusion-reflection imaging analysis with that from the traditional gas chromatography spectrometer with thermal conductivity detectors, a colorimetric diffusion-reflection imaging method was confirmed to be reliable and accurate in acrolein analysis.

High-throughput reactor system with individual temperature control for the investigation of monolith catalysts

A high-throughput parallel reactor system has been designed and constructed to improve the reliability of results from large diameter catalysts such as monoliths. The system, which is expandable, consists of eight quartz reactors, 23.5 mm in diameter. The eight reactors were designed with separate K type thermocouples and radiant heaters, allowing for the independent measurement and control of each reactor temperature. This design gives steady state temperature distributions over the eight reactors within 0.5 degrees C of a common setpoint from 50 to 700 degrees C. Analysis of the effluent from these reactors is performed using rapid-scan Fourier transform infrared (FTIR) spectroscopic imaging. The integration of this technique to the reactor system allows a chemically specific, truly parallel analysis of the reactor effluents with a time resolution of approximately 8 s. The capabilities of this system were demonstrated via investigation of catalyst preparation conditions on the direct epoxidation of ethylene, i.e., on the ethylene conversion and the ethylene oxide selectivity. The ethylene, ethylene oxide, and carbon dioxide concentrations were calibrated based on spectra from FTIR imaging using univariate and multivariate chemometric techniques. The results from this analysis showed that the calcination conditions significantly affect the ethylene conversion, with a threefold increase in the conversion when the catalyst was calcined for 3 h versus 12 h at 400 degrees C.

Discovery of New Heterogeneous Catalysts for the Selective Oxidation of Propane to Acrolein

Combinatorial synthesis and screening technique have been applied to investigate the catalytic activity and selectivity of ternary and quaternary mixed-metal oxide catalysts for the selective oxidation of propane. The catalyst libraries were prepared via a modified sol-gel method using a synthesis robot and library design software, and examined for the catalytic activities in a simple high-throughput reactor system connected to a mass spectrometer for product analysis. Ternary Mo-Cr-Te, V-Cr-Sb, and Mo-V-Cr catalysts have been selected for potential candidate by composition spread approach. In a next generation composition spread library, the composition space of these three ternary compositions was sampled. Screening of this 198-member library provided substantial evidence that each ternary system has its own optimum composition where acrolein formation is highest. In addition, the composition space of the quaternary reference system Mo-V-Te-Nb mixed-oxides has also been prepared and sampled.

Combinatorial discovery of new autoreduction catalysts for the CO 2 reforming of methane

High-throughput synthesis and screening techniques were used in the search for and optimization of new autoreduction catalysts for the CO 2 reforming of methane. Diverse libraries had been synthesized via three different modified sol–gel methods using a synthesis robot and library design software. The catalyst libraries were screened for catalytic activity and stability in a simple high-throughput reactor system at 600 °C connected to a micro-gas chromatograph for product analysis. During generations 1 and 2, more than 5000 highly diverse mixed oxides were tested for potential catalytic activity. Ni 10Ce 90O x demonstrated effective activity and stability among nonprecious metal catalysts without a prereduction step. In a conventional study, two advantages (i.e., rapid startup operation and high coking resistance) of Ni 10Ce 90O x were noted relative to the well-known Ni/Al 2O 3, but deactivation was recognized. To reduce deactivation of Ni 10Ce 90O x , catalyst libraries with additional dopants were prepared and examined during generations 3 and 4. Among these, (Al 5, Al 15, Zr 15)Ni 10Ce 90− y O x , in which metal nitrate was used as a dopant precursor, and (Al 15, Zr 5, Zr 15)Ni 10Ce 90− y O x , in which metal alkoxide was used, exhibited comparable activity and strongly reduced deactivation compared with Ni 10Ce 90O x . Good performance of the best new catalysts, particularly Al 15Ni 10Ce 75O x , in which aluminium alkoxide was used as a dopant precursor, and Zr 15Ni 10Ce 75O x , in which zirconium dinitrate oxide was used, was found in high-throughput studies and confirmed in conventional experiments.

A rational design of alkyl-aromatics dealkylation–transalkylation catalysts using C8 and C9 alkyl-aromatics as reactants

A catalyst has been designed to optimize the dealkylation of ethyl and propyl aromatics while producing the transalkylation of tri- and tetramethylbenzene with toluene in order to maximize xylenes and benzene when processing heavy reformate. Conversion of model ethyl-aromatics under realistic transalkylation conditions has been studied over two reference catalysts and seven different acid zeolites including topologies with channel systems containing 10 MR, 12 MR, and 10 + 12 MR. Catalytic testing was accomplished by means of a high-throughput reactor system. It has been found that zeolite structure has a direct influence on the ethyl dealkylation/transalkylation activity, increasing the ethylbenzene conversion and dealkylation selectivity when decreasing the zeolite pore volume. Moreover, Re/IM-5 and, specially, Re/ZSM-5 zeolites show an excellent dealkylation activity. Ethylbenzene undergoes different bimolecular reactions giving as primary products either benzene and diethylbenzene or toluene and ethyltoluene, each reaction involving a different biphenylic intermediate and the selectivity toward each mechanism is directly influenced by the zeolite pore size and geometry.

99/03907 The temperature—entropy chart for hydrogen engines: Abdelfattah, A. I. I. Alexandria Eng. J., 1998, 37, (5), A231–A236

A catalyst has been designed to optimize the dealkylation of ethyl and propyl aromatics while producing the transalkylation of tri- and tetramethylbenzene with toluene in order to maximize xylenes and benzene when processing heavy reformate. Conversion of model ethyl-aromatics under realistic transalkylation conditions has been studied over two reference catalysts and seven different acid zeolites including topologies with channel systems containing 10 MR, 12 MR, and 10 + 12 MR. Catalytic testing was accomplished by means of a high-throughput reactor system. It has been found that zeolite structure has a direct influence on the ethyl dealkylation/transalkylation activity, increasing the ethylbenzene conversion and dealkylation selectivity when decreasing the zeolite pore volume. Moreover, Re/IM-5 and, specially, Re/ZSM-5 zeolites show an excellent dealkylation activity. Ethylbenzene undergoes different bimolecular reactions giving as primary products either benzene and diethylbenzene or toluene and ethyltoluene, each reaction involving a different biphenylic intermediate and the selectivity toward each mechanism is directly influenced by the zeolite pore size and geometry.

97/02433 Mathematical modeling of char reactivity in Ar-02 and CO2-O2 mixtures

A catalyst has been designed to optimize the dealkylation of ethyl and propyl aromatics while producing the transalkylation of tri- and tetramethylbenzene with toluene in order to maximize xylenes and benzene when processing heavy reformate. Conversion of model ethyl-aromatics under realistic transalkylation conditions has been studied over two reference catalysts and seven different acid zeolites including topologies with channel systems containing 10 MR, 12 MR, and 10 + 12 MR. Catalytic testing was accomplished by means of a high-throughput reactor system. It has been found that zeolite structure has a direct influence on the ethyl dealkylation/transalkylation activity, increasing the ethylbenzene conversion and dealkylation selectivity when decreasing the zeolite pore volume. Moreover, Re/IM-5 and, specially, Re/ZSM-5 zeolites show an excellent dealkylation activity. Ethylbenzene undergoes different bimolecular reactions giving as primary products either benzene and diethylbenzene or toluene and ethyltoluene, each reaction involving a different biphenylic intermediate and the selectivity toward each mechanism is directly influenced by the zeolite pore size and geometry.

Additions of acetaldehyde to ethylene in the presence of composite catalysts: G. N. Gvozdovskii, Yu. N. Koshelev, B. P. Tarasov, T. A. Marakayev, A. V. Devekki and D. V. Mushenko, Neftekhimiya 25, No. 2, 218–223, 1985

A catalyst has been designed to optimize the dealkylation of ethyl and propyl aromatics while producing the transalkylation of tri- and tetramethylbenzene with toluene in order to maximize xylenes and benzene when processing heavy reformate. Conversion of model ethyl-aromatics under realistic transalkylation conditions has been studied over two reference catalysts and seven different acid zeolites including topologies with channel systems containing 10 MR, 12 MR, and 10 + 12 MR. Catalytic testing was accomplished by means of a high-throughput reactor system. It has been found that zeolite structure has a direct influence on the ethyl dealkylation/transalkylation activity, increasing the ethylbenzene conversion and dealkylation selectivity when decreasing the zeolite pore volume. Moreover, Re/IM-5 and, specially, Re/ZSM-5 zeolites show an excellent dealkylation activity. Ethylbenzene undergoes different bimolecular reactions giving as primary products either benzene and diethylbenzene or toluene and ethyltoluene, each reaction involving a different biphenylic intermediate and the selectivity toward each mechanism is directly influenced by the zeolite pore size and geometry.