Continuous Hydrothermal Flow Synthesis System Research Articles

High Throughput Synthesis and Screening of Oxygen Reduction Catalysts in the MTiO3 (M = Ca, Sr, Ba) Perovskite Phase Diagram.

A library of 66 perovskite BaxSryCazTiO3 (x + y + z = 1) samples (ca. three grams per sample) was made in ca. 14 h using a high-throughput continuous hydrothermal flow synthesis system. The as-synthesized samples were collected from the outlet of the process and then cleaned and freeze-dried before being evaluated individually as oxygen reduction catalysts using a rotating disk electrode testing technique. To establish any correlations between physical and electrochemical characterization data, the as-synthesized samples were investigated using analytical methods including BET surface area, powder X-ray diffraction (PXRD) and in selected cases, transmission electron microscopy (TEM). The aforementioned approach was validated as being able to quickly identify oxygen reduction catalysts from new libraries of electrocatalysts.

A numerical study on heat transfer enhancement and design of a heat exchanger with porous media in continuous hydrothermal flow synthesis system

Abstract The aim of this study is to use a new configuration of porous media in a heat exchanger in continuous hydrothermal flow synthesis (CHFS) system to enhance the heat transfer and minimize the required length of the heat exchanger. For this purpose, numerous numerical simulations are performed to investigate performance of the system with porous media. First, the numerical simulation for the heat exchanger in CHFS system is validated by experimental data. Then, porous media is added to the system and six different thicknesses for the porous media are examined to obtain the optimum thickness, based on the minimum required length of the heat exchanger. Finally, by changing the flow rate and inlet temperature of the product as well as the cooling water flow rate, the minimum required length of the heat exchanger with porous media for various inlet conditions is assessed. The investigations indicate that using porous media with the proper thickness in the heat exchanger increases the cooling rate of the product by almost 40% and reduces the required length of the heat exchanger by approximately 35%. The results also illustrate that the most proper thickness of the porous media is approximately equal to 90% of the product tube's thickness. Results of this study lead to design a porous heat exchanger in CHFS system for various inlet conditions.

Rapid hydrothermal flow synthesis and characterisation of carbonate- and silicate-substituted calcium phosphates

A range of crystalline and nano-sized carbonate- and silicate-substituted hydroxyapatite has been successfully produced by using continuous hydrothermal flow synthesis technology. Ion-substituted calcium phosphates are better candidates for bone replacement applications (due to improved bioactivity) as compared to phase-pure hydroxyapatite. Urea was used as a carbonate source for synthesising phase pure carbonated hydroxyapatite (CO3-HA) with ≈5 wt% substituted carbonate content (sample 7.5CO3-HA) and it was found that a further increase in urea concentration in solution resulted in biphasic mixtures of carbonate-substituted hydroxyapatite and calcium carbonate. Transmission electron microscopy images revealed that the particle size of hydroxyapatite decreased with increasing urea concentration. Energy-dispersive X-ray spectroscopy result revealed a calcium deficient apatite with Ca:P molar ratio of 1.45 (±0.04) in sample 7.5CO3-HA. For silicate-substituted hydroxyapatite (SiO4-HA) silicon acetate was used as a silicate ion source. It was observed that a substitution threshold of ∼1.1 wt% exists for synthesis of SiO4-HA in the continuous hydrothermal flow synthesis system, which could be due to the decreasing yields with progressive increase in silicon acetate concentration. All the as-precipitated powders (without any additional heat treatments) were analysed using techniques including Transmission electron microscopy, X-ray powder diffraction, Differential scanning calorimetry, Thermogravimetric analysis, Raman spectroscopy and Fourier transform infrared spectroscopy.

Numerical Simulation of Fluid Flow and Heat Transfer in a Counter-Current Reactor System for Nanomaterial Production

Continuous hydrothermal flow synthesis (CHFS) systems can provide high quality fine nanoparticles. However, optimisation of the CHFS system including the reactor and heat exchanger design, and their scaling-up for commercial applications have not been studied and cannot be achieved only through laboratory and pilot plant experiments. CFD modelling techniques are being widely used to simulate fluid field, heat and mass transfer in a lot of industrial process equipment. However, the application of CFD to model CHFS systems is still rare. This paper employs CFD methodology to simulate fluid flow and heat transfer in a counter-current reactor and a tubular heat exchanger of a laboratory-scale CHFS system for the production of TiO2 nanoparticles. The distributions of flow and heat transfer variables such as velocity and temperature in both units are obtained using ANSYS Fluent package. The tracer concentration profile is also simulated via solving the species equations to investigate the mixing behaviour in the counter-current reactor. Temperature distributions at different locations in a counter-current reactor and a tubular heat exchanger of a CHFS system were obtained experimentally. The simulated temperatures in both the reactor and the heat exchanger are compared with the available experimental data, which reveals that a good level of agreement is achieved.

Numerical modelling of hydrothermal fluid flow and heat transfer in a tubular heat exchanger under near critical conditions

Continuous hydrothermal flow synthesis processes are of interest for the manufacture of nanoparticle metal oxides. In such processes, nanoparticle nuclei (in a slurry) which are initially formed, may continue to grow and agglomerate to generate larger particles as they pass through the synthesis apparatus. These processes can widen the size distribution and also affect the ultimate particle shape in the recovered product. Therefore, fast cooling or quenching the initial nanoparticle slurry using a highly efficient heat exchanger may minimise or stop further crystallisation/agglomeration processes. This may be achieved by optimising the design of the heat exchanger based on detailed examination of flow patterns and heat transfer profiles using a computational fluid dynamics (CFD) modelling approach. The predicted flow and heat transfer patterns in the heat exchanger can also provide detailed information for the identification of any heat transfer deterioration or hot spots where further reactions may occur. This paper employs a CFD modelling approach to simulate the heat transfer processes in a tubular heat exchanger of a continuous hydrothermal flow synthesis system and also to examine the effect of various operating conditions, including inlet temperature and flowrate of hot slurry and inlet flowrate of cooling water, on the fluid and thermal features in the heat exchanger. The simulated results show that the predicted temperature and heat transfer coefficient are in good agreement with experimental measurements.

Direct syntheses of La n+1Ni nO 3n+1 phases ( n=1, 2, 3 and ∞) from nanosized co-crystallites

A new direct route for the “bottom up” syntheses of phases in the La n +1Ni n O 3 n +1 series ( n=1, 2, 3 and ∞) has been achieved via single-step heat treatments of nanosized co-crystallized precursors. The co-crystallized precursors were prepared using a continuous hydrothermal flow synthesis system that uses a superheated water flow at ca. 400 °C and 24.1 MPa to produce nanoparticulate slurries. Overall, a significant reduction in time and number of steps for the syntheses of La 3Ni 2O 7 and La 4Ni 3O 10 was achieved compared with more conventional synthesis methods, which typically require multiple homogenization and reheating steps over several days.

Synthesis and characterisation of magnesium substituted calcium phosphate bioceramic nanoparticles made via continuous hydrothermal flow synthesis

Continuous hydrothermal flow synthesis (CHFS) technology has been used as an efficient and direct route to produce a range of largely crystalline magnesium substituted calcium phosphate bioceramics. Initially, magnesium substituted hydroxyapatite, Mg-HA, according to the formula [Ca10−xMgx(PO4)6(OH)2] was prepared in the CHFS system for x = 0.2 [where x:(10 − x) is the Mg:Ca ratio used in the reagents]. Biphasic mixtures of Mg-HA and Mg-whitlockite were obtained corresponding to x values in the range x = 0.4–1.6. The direct synthesis of phase pure crystalline Mg-whitlockite [based on the formula (Ca3−yMgy(HPO4)z(PO4)2−2z/3] was also achieved using the CHFS system for the range y = 0.7–1.6 (this corresponds to the range x = 1.6–5.3). With increasing substitution of magnesium for calcium, the material became ever more amorphous and the BET surface area generally increased. All the as-precipitated powders (without any additional heat treatments) were analyzed using techniques including X-ray powder diffraction, Raman spectroscopy and Fourier transform infra-red spectroscopy. Transmission electron microscopy (TEM) images revealed that in the case of y = 1.2, the Mg-whitlockite material comprised of ca. 28 nm sized spheres. The use of the CHFS system in this context facilitated rapid production of combinations of particle properties (crystallinity, size, shape) that were hitherto unobtainable in a single step process.

Direct Syntheses of Mixed Ion and Electronic Conductors La4Ni3O10 and La3Ni2O7 from Nanosized Coprecipitates

Nanoparticle coprecipitates of lanthanum hydroxide and nickel hydroxide were synthesized in a continuous hydrothermal flow synthesis system. Two such coprecipitates with the appropriate La:Ni molar ratios were subsequently directly converted to phase-pure La4Ni3O10 and La3Ni2O7, respectively, via a single heat-treatment step in each case.

Direct Synthesis of Nanosized NiCo2O4Spinel and Related Compounds via Continuous Hydrothermal Synthesis Methods

A series of crystalline homometallic and heterometallic cobalt and nickel hydroxides and oxides were prepared using a continuous hydrothermal flow synthesis system. In all syntheses, the relevant m...